TWI762536B - Heat-shrinkable polyester label, package, and method for producing heat-shrinkable polyester label - Google Patents

Heat-shrinkable polyester label, package, and method for producing heat-shrinkable polyester label Download PDF

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Publication number
TWI762536B
TWI762536B TW106143366A TW106143366A TWI762536B TW I762536 B TWI762536 B TW I762536B TW 106143366 A TW106143366 A TW 106143366A TW 106143366 A TW106143366 A TW 106143366A TW I762536 B TWI762536 B TW I762536B
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Taiwan
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heat
polyester
solvent
film
shrinkable polyester
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TW106143366A
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Chinese (zh)
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TW201835063A (en
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丸山裕子
春田雅幸
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日商東洋紡股份有限公司
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06—Making preforms having internal stresses, e.g. plastic memory
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4895—Solvent bonding, i.e. the surfaces of the parts to be joined being treated with solvents, swelling or softening agents, without adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B29C66/431—Joining the articles to themselves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B29C66/432—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms
    • B29C66/4322—Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms by joining a single sheet to itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/0878—Shrunk on the bottle
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2667/00—Use of polyesters or derivatives thereof for preformed parts, e.g. for inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0049—Heat shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/744—Labels, badges, e.g. marker sleeves
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F2003/0272—Labels for containers
    • G09F2003/0273—Labels for bottles, flasks

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

本發明提供一種具有即便膜之厚度較薄亦不會引起溶劑穿透之溶劑黏接部的熱收縮性聚酯系標籤及包裝體。尤其提供一種具有如下溶劑黏接部之熱收縮性聚酯系標籤及包裝體，上述溶劑黏接部係即便於已高速化之造管步驟中或者即便是使用了較多之PET瓶再利用原料之熱收縮性聚酯系膜亦可穩定地獲得高剝離強度。 The present invention provides a heat-shrinkable polyester-based label and a package having a solvent-bonded portion that does not cause solvent penetration even if the film is thin. In particular, there is provided a heat-shrinkable polyester-based label and packaging body having the following solvent-bonded parts, the solvent-bonded parts are reused raw materials even in the process of high-speed pipe making or even if more PET bottles are used The heat-shrinkable polyester film can also obtain high peel strength stably.

本發明之熱收縮性聚酯系標籤係熱收縮性聚酯系膜之兩端部利用溶劑組成物黏接而成之管狀之熱收縮性聚酯系標籤，前述溶劑組成物係至少包含1,3-二氧雜環戊烷及/或四氫呋喃(THF)與聚酯之溶劑組成物，前述黏接部之剝離強度為2N/15mm以上。 The heat-shrinkable polyester label of the present invention is a tubular heat-shrinkable polyester label in which both ends of the heat-shrinkable polyester film are bonded by a solvent composition, and the solvent composition comprises at least 1, In the solvent composition of 3-dioxolane and/or tetrahydrofuran (THF) and polyester, the peel strength of the aforementioned adhesive part is 2N/15mm or more.

Description

熱收縮性聚酯系標籤、包裝體以及熱收縮性聚酯系標籤的製造方法 Heat-shrinkable polyester label, package, and method for producing heat-shrinkable polyester label

本發明係關於一種藉由將熱收縮性聚酯系膜捲成管狀並利用溶劑將前述膜之兩端部彼此黏接而形成的熱收縮性聚酯系標籤，更詳細而言，係關於一種即便形成標籤之膜之厚度較薄亦不易引起溶劑黏接部中之溶劑之過度浸透的熱收縮性聚酯系標籤。而且，係關於一種即便使用較多之結晶性較高之聚對苯二甲酸乙二酯原料作為膜原料，溶劑黏接部之剝離強度亦較高的熱收縮性聚酯系標籤。 The present invention relates to a heat-shrinkable polyester-based label formed by rolling a heat-shrinkable polyester-based film into a tubular shape and bonding both ends of the film with a solvent, and more specifically, to a heat-shrinkable polyester-based label. A heat-shrinkable polyester-based label that does not easily cause excessive penetration of the solvent in the solvent-bonded portion even if the thickness of the film forming the label is thin. Furthermore, it relates to a heat-shrinkable polyester label having a high peel strength of a solvent-bonded portion even if a large amount of a polyethylene terephthalate raw material having high crystallinity is used as a film raw material.

近年來，於兼備玻璃瓶或塑膠瓶等之保護與商品之顯示的標籤包裝、蓋封、多件組合裝(multipack)等之用途中，由耐熱性高、焚燒容易且耐溶劑性優異之聚酯系熱收縮性膜所獲得之熱收縮性聚酯系標籤被廣泛利用，存在伴隨PET(polyethylene terephthalate；聚對苯二甲酸乙二酯)瓶容器等之增大而使用量增加之傾向。 In recent years, in the application of label packaging, cap sealing, multipack, etc., which combines the protection of glass bottles or plastic bottles with the display of products, the polymer has high heat resistance, easy incineration and excellent solvent resistance. Heat-shrinkable polyester-based labels obtained from ester-based heat-shrinkable films are widely used, and there is a tendency that the usage amount increases with the increase of PET (polyethylene terephthalate; polyethylene terephthalate) bottle containers and the like.

然而，熱收縮性標籤由於使用後會成為垃圾，故最近考慮到環境方面需要減少垃圾量，從而開始使用厚度較薄之熱收縮性標籤(經薄壁化之熱收縮性標籤)。而且，為了應對各種容器，收縮率高之熱收縮膜之需求較多。因此， 存在使用非晶量增加之原料製造熱收縮膜之情況增加之傾向。 However, since heat-shrinkable labels become waste after use, recently, in consideration of the environmental need to reduce the amount of waste, thinner heat-shrinkable labels (thin-walled heat-shrinkable labels) have been used. Moreover, in order to cope with various containers, there are many demands for heat-shrinkable films with high shrinkage rates. Therefore, there is a tendency that a heat shrinkable film is produced using a raw material having an increased amount of amorphous.

而且，有為了進一步環保而增加了PET瓶再利用原料之比率之熱收縮性聚酯系膜。 In addition, there is a heat-shrinkable polyester-based film in which the ratio of the recycled raw material of the PET bottle is increased for further environmental protection.

且說，為了由熱收縮性膜形成管狀標籤，需要將膜之寬度方向一端部重疊於另一端部而進行固定。作為該固定方法，以往使用的是溶劑黏接法(專利文獻1、2)或使用黏接劑之方法(專利文獻3)等。上述方法中溶劑黏接法能夠高速地加工成管狀標籤，從而得到廣泛利用。 In addition, in order to form a tubular label from a heat-shrinkable film, it is necessary to overlap and fix one end part in the width direction of the film on the other end part. As the fixing method, a solvent bonding method (Patent Documents 1 and 2), a method using an adhesive (Patent Document 3), and the like have been conventionally used. Among the above-mentioned methods, the solvent bonding method can be processed into a tubular label at a high speed, and thus is widely used.

利用該溶劑黏接法將熱收縮性聚酯系膜之面彼此加工成管狀標籤之步驟(造管(tubing)步驟)中，為了提高生產效率而實現成本降低，正推進高速化。高速之造管步驟中，為了穩定地獲得高剝離強度(黏接強度)之溶劑黏接部，使一般被用作黏接溶劑之1,3-二氧雜環戊烷之塗佈量增多即可，但若增多1,3-二氧雜環戊烷之塗佈量，則於厚度較薄且非晶原料較多之熱收縮性聚酯系膜之情形時，溶劑會自塗佈面側浸透至膜背面側(溶劑穿透)，從而背面亦附著有溶劑。而且，於將溶劑黏接後之管狀標籤呈卷狀捲繞時管狀標籤會被壓平，當在溶劑黏接部引起了溶劑穿透時，存在如下情況：與溶劑黏接部之裡側接觸之標籤黏接而無法作為管發揮功能，或引起黏連而無法將卷解開。 In the step (tubing step) of processing the surfaces of the heat-shrinkable polyester films into tubular labels by this solvent bonding method, in order to improve production efficiency and achieve cost reduction, speeding up is being promoted. In the high-speed pipe-making process, in order to stably obtain a solvent-bonded part with high peel strength (bonding strength), the coating amount of 1,3-dioxolane, which is generally used as a bonding solvent, is increased. Yes, but if the coating amount of 1,3-dioxolane is increased, in the case of a heat-shrinkable polyester film with a thin thickness and a large amount of amorphous raw materials, the solvent will flow from the coating surface side It penetrates to the back surface side of the film (solvent penetration), and the solvent adheres to the back surface as well. In addition, when the tubular label after the solvent bonding is rolled in a roll shape, the tubular label is flattened. When the solvent is penetrated in the solvent bonding portion, there is a case where it contacts the inner side of the solvent bonding portion. The label sticks and fails to function as a tube, or causes sticking and the roll cannot be unwound.

另一方面，若為了不使溶劑穿透而減少1,3-二氧雜環戊烷之塗佈量，則於已高速化之造管步驟中有如下不良：1,3-二氧雜環戊烷之塗佈量容易不均，於塗佈量減少之情形時無法獲得充分之剝離強度。為了不溶劑穿透而使用四 氫呋喃(tetrahydrofuran；THF)來代替1,3-二氧雜環戊烷之情形亦同樣地，於已高速化之造管步驟中有如下不良：THF之塗佈量容易不均，於塗佈量減少之情形時無法獲得充分之剝離強度。 On the other hand, if the coating amount of 1,3-dioxolane is reduced in order to prevent the penetration of the solvent, there are the following disadvantages in the pipe-making process that has been accelerated: 1,3-dioxane The coating amount of pentane tends to be uneven, and sufficient peel strength cannot be obtained when the coating amount is reduced. In the case of using tetrahydrofuran (THF) instead of 1,3-dioxolane in order to prevent the penetration of the solvent, there are the following disadvantages in the high-speed pipe making process: the amount of THF applied is easy Uneven, when the coating amount is reduced, sufficient peel strength cannot be obtained.

而且，為了環保，使用較多之PET瓶再利用原料之熱收縮性聚酯系膜之需求增高。然而，PET瓶再利用原料係結晶性高之聚對苯二甲酸乙二酯原料，因而耐化學品性優異，對於專利文獻1、2所示之溶劑即1,3-二氧雜環戊烷而言，存在黏接部之剝離強度不足之問題。 Moreover, in order to protect the environment, the demand for heat-shrinkable polyester-based films that use more PET bottles to reuse raw materials is increasing. However, since the PET bottle reuses the raw material of polyethylene terephthalate with high crystallinity, it has excellent chemical resistance. In other words, there is a problem that the peel strength of the adhesive portion is insufficient.

因此，發明出如下方法，即，利用1,3-二氧雜環戊烷及與1,3-二氧雜環戊烷相溶之有機溶劑之混合溶劑進行黏接(專利文獻4)。然而，為了防止溶劑穿透，需要於溶劑黏接加工前對溶劑黏接部塗佈不良溶劑並使其乾燥之步驟(預處理)，從而存在作業效率變差之問題。而且，作為省略前述預處理之方法，雖有利用1,3-二氧雜環戊烷與聚酯之不良溶劑之混合溶液進行黏接之方法，但若不良溶劑之量較少則無法獲得抑制溶劑穿透之效果，若過多則已高速化之造管步驟中無法獲得充分之剝離強度，因此必須根據膜之種類而調整1,3-二氧雜環戊烷與不良溶劑混合比率。 Therefore, a method of bonding using a mixed solvent of 1,3-dioxolane and an organic solvent compatible with 1,3-dioxolane has been invented (Patent Document 4). However, in order to prevent the penetration of the solvent, a step (pretreatment) of applying a poor solvent to the solvent-bonded portion and drying it is required before the solvent-bonding process, so that there is a problem that the working efficiency is deteriorated. In addition, as a method of omitting the above-mentioned pretreatment, there is a method of bonding using a mixed solution of 1,3-dioxolane and a poor solvent of polyester, but if the amount of poor solvent is small, inhibition cannot be obtained. If the effect of solvent penetration is too large, sufficient peel strength cannot be obtained in the pipe-making process which has been accelerated. Therefore, the mixing ratio of 1,3-dioxolane and poor solvent must be adjusted according to the type of film.

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

專利文獻1：專利第3075019號公報。 Patent Document 1: Patent No. 3075019.

專利文獻2：專利第3452021號公報。 Patent Document 2: Patent No. 3452021.

專利文獻3：日本專利特開2014-43520號公報。 Patent Document 3: Japanese Patent Laid-Open No. 2014-43520.

專利文獻4：國際公開第2016/039133號。 Patent Document 4: International Publication No. 2016/039133.

本發明之課題在於提供具有如下溶劑黏接部之熱收縮性聚酯系標籤及包裝體，該溶劑黏接部係即便於膜之厚度較薄且非晶原料較多之情形時亦不易引起溶劑穿透，本發明之課題在於尤其提供一種具有如下溶劑黏接部之熱收縮性聚酯系標籤及包裝體，該溶劑黏接部係即便於已高速化之造管步驟中或者即便是使用較多之PET瓶再利用原料之熱收縮性聚酯系膜亦可穩定地獲得高剝離強度。 An object of the present invention is to provide a heat-shrinkable polyester-based label and a package having a solvent-bonded portion that is less likely to cause a solvent even when the film thickness is thin and there are many amorphous materials Through penetration, the subject of the present invention is to especially provide a heat-shrinkable polyester label and packaging body having the following solvent-bonded parts, the solvent-bonded parts are used even in the process of high-speed pipe making or even when using relatively The heat-shrinkable polyester-based film that uses many PET bottles as raw materials can also obtain high peel strength stably.

本發明者關於上述課題反復進行了積極研究，結果發現藉由使用由特定種類之化合物之組合構成的溶劑組成物可解決上述課題，從而完成本發明。 The inventors of the present invention have repeatedly conducted active studies on the above-mentioned problems, and as a result, they have found that the above-mentioned problems can be solved by using a solvent composition composed of a combination of specific types of compounds, and completed the present invention.

亦即，本發明為以下構成。 That is, the present invention has the following configuration.

1.一種熱收縮性聚酯系標籤，其係熱收縮性聚酯系膜之兩端部彼此利用溶劑組成物黏接而成之管狀之熱收縮性聚酯系標籤，前述溶劑組成物係至少包含1,3-二氧雜環戊烷及/或四氫呋喃(THF)與聚酯之溶劑組成物，前述黏接部之剝離強度為2N/15mm以上。 1. A heat-shrinkable polyester-based label, which is a tubular heat-shrinkable polyester-based label in which both ends of a heat-shrinkable polyester-based film are bonded with a solvent composition, wherein the solvent composition is at least In the solvent composition comprising 1,3-dioxolane and/or tetrahydrofuran (THF) and polyester, the peel strength of the aforementioned adhesive portion is 2N/15mm or more.

2.如1所記載之熱收縮性聚酯系標籤，其中前述溶劑組成物中所含之聚酯之含量為1質量%以上40質量%以 下。 2. The heat-shrinkable polyester label according to 1, wherein the content of the polyester contained in the solvent composition is 1 mass % or more and 40 mass % or less.

3.如1或2中任一項所記載之熱收縮性聚酯系標籤，其中前述熱收縮性聚酯系膜之厚度為5μm以上60μm以下。 3. The heat-shrinkable polyester-based label according to any one of 1 or 2, wherein the thickness of the heat-shrinkable polyester-based film is 5 μm or more and 60 μm or less.

4.如1至3中任一項所記載之熱收縮性聚酯系標籤，其中包含至少表層具有前述熱收縮性聚酯系膜之積層膜。 4. The heat-shrinkable polyester-based label according to any one of 1 to 3, comprising a laminate film having the heat-shrinkable polyester-based film on at least a surface layer thereof.

5.一種包裝體，係於包裝對象物之外周之至少一部分具有如前述1至4中任一項所記載之熱收縮性聚酯系標籤。 5. A package comprising the heat-shrinkable polyester label according to any one of 1 to 4 above on at least a part of the outer periphery of an object to be packaged.

6.一種熱收縮性聚酯系標籤的製造方法，係利用至少包含1,3-二氧雜環戊烷及/或四氫呋喃(THF)與聚酯之溶劑組成物，將前述膜之兩端部重合並黏接。 6. A method for producing a heat-shrinkable polyester label, comprising at least a solvent composition comprising 1,3-dioxolane and/or tetrahydrofuran (THF) and polyester, to separate both ends of the film. Overlap and glue.

7.一種熱收縮性聚酯系標籤用溶劑組成物，係至少包含1,3-二氧雜環戊烷及/或四氫呋喃(THF)與聚酯之黏度小於100mPa‧s之溶劑組成物，用於藉由該溶劑組成物將熱收縮性膜黏接而作成熱收縮性聚酯系標籤。 7. A solvent composition for a heat-shrinkable polyester label, comprising at least 1,3-dioxolane and/or tetrahydrofuran (THF) and a solvent composition with a polyester viscosity of less than 100 mPa·s, using A heat-shrinkable polyester label is produced by bonding the heat-shrinkable film with the solvent composition.

根據本發明，提供具有如下溶劑黏接部之熱收縮性聚酯系標籤及包裝體，該溶劑黏接部係即便於熱收縮性聚酯系膜之厚度較薄且非晶原料較多之情形時亦不會引起溶劑穿透，且，即便於已高速化之造管步驟中或者即便是使用較多之結晶性高之聚對苯二甲酸乙二酯原料之熱收縮性聚酯系膜亦可穩定地獲得高剝離強度。 According to the present invention, there is provided a heat-shrinkable polyester-based label and a package having a solvent-bonded portion, which is formed even when the thickness of the heat-shrinkable polyester-based film is thin and the amount of amorphous raw materials is large. It will not cause the penetration of the solvent, and even in the high-speed pipe making step or even in the heat-shrinkable polyester film that uses a large amount of polyethylene terephthalate raw material with high crystallinity High peel strength can be obtained stably.

本發明之熱收縮性聚酯系標籤係藉由將熱收縮性聚酯系膜之兩端部彼此重疊並利用溶劑組成物黏接所形成的管狀之熱收縮性聚酯系標籤。此處，端部是指寬度方向(沿著長度方向之方向)的端部，是指包含自端部算起的20mm以內之部分之位置。 The heat-shrinkable polyester label of the present invention is a tubular heat-shrinkable polyester label formed by overlapping both ends of the heat-shrinkable polyester film and adhering with a solvent composition. Here, the end portion refers to the end portion in the width direction (the direction along the longitudinal direction), and refers to the position including the portion within 20 mm from the end portion.

而且，本發明之熱收縮性聚酯系膜中，不僅包含僅由1層聚酯構成之膜，亦包含聚酯/聚酯以外之樹脂/聚酯這樣的積層構成之膜且外側之層亦為聚酯系膜之積層膜。 Further, the heat-shrinkable polyester film of the present invention includes not only a film composed of only one layer of polyester, but also a film composed of a laminate of polyester/polyester other than resin/polyester, and an outer layer is also included. It is a laminated film of polyester film.

本發明中，提供如下之聚酯系標籤，即，藉由使溶劑組成物包含1,3-二氧雜環戊烷及/或四氫呋喃(THF)與聚酯之雙方，即便於熱收縮性聚酯系膜之厚度較薄且非晶原料較多之情形時亦不會引起溶劑穿透，且，於已高速化之造管步驟中，即便是使用較多之結晶性高之聚對苯二甲酸乙二酯原料之熱收縮性聚酯系膜，溶劑黏接部之剝離強度亦高。 In the present invention, there is provided a polyester-based label that can be used in a heat-shrinkable polymer even when the solvent composition contains both 1,3-dioxolane and/or tetrahydrofuran (THF) and polyester. When the thickness of the ester film is thin and there are many amorphous raw materials, it will not cause the penetration of the solvent, and in the pipe-making process that has been speeded up, even if more polyterephthalene with high crystallinity is used The heat-shrinkable polyester film of ethylene formate raw material also has high peel strength of the solvent-bonded part.

1,3-二氧雜環戊烷係聚酯之良溶劑，因使聚酯系膜迅速地溶解，故所獲得之溶劑黏接部具有高剝離強度。然而，含有多於25質量%之作為結晶性較高之PET瓶再利用原料之主成分的聚對苯二甲酸乙二酯之聚酯系膜不易溶解於1,3-二氧雜環戊烷，僅利用1,3-二氧雜環戊烷進行溶劑黏接，並無法獲得充分之剝離強度。 As a good solvent for 1,3-dioxolane-based polyester, since the polyester-based film can be rapidly dissolved, the obtained solvent-bonded part has high peel strength. However, the polyester-based film containing more than 25% by mass of polyethylene terephthalate, which is the main component of the recycled raw material for PET bottles with high crystallinity, is not easily dissolved in 1,3-dioxolane , only using 1,3-dioxolane for solvent bonding cannot obtain sufficient peel strength.

另一方面，藉由使本發明之溶劑組成物所含有之聚酯 含有能夠成為非晶質成分之1種以上之單體成分，從而變得容易因有機溶劑或熱而溶解，因此可較佳地用作黏接劑，即便是含有多於25質量%的前述聚對苯二甲酸乙二酯之聚酯系膜，只要使用本發明之包含1,3-二氧雜環戊烷與前述聚酯之溶劑組成物，便可獲得高剝離強度。而且，藉由利用熱使前述聚酯熔解從而用作熱熔劑，聚酯系膜之黏接成為可能，但於使熱收縮性聚酯系膜黏接之情形時，因熱熔劑之熱，聚酯系膜收縮而出現皺褶，從而容易發生外觀不良，且因黏度高，故於高速之造管步驟中，難以穩定地塗佈固定量之聚酯系膜。 On the other hand, by making the polyester contained in the solvent composition of the present invention contain one or more monomer components capable of becoming an amorphous component, it is easy to dissolve in an organic solvent or heat, which is preferable. Even if it is a polyester film containing more than 25% by mass of the above-mentioned polyethylene terephthalate, as long as the 1,3-dioxolane of the present invention is used and the above-mentioned poly The solvent composition of ester can obtain high peel strength. In addition, the polyester film can be adhered by melting the polyester by heat to be used as a hot melt, but in the case of adhering a heat-shrinkable polyester film, the heat of the hot melt causes the adhesion of the polyester film. Ester-based film shrinks to form wrinkles, which is prone to poor appearance, and because of high viscosity, it is difficult to stably coat a fixed amount of polyester-based film during high-speed pipe-making steps.

亦即，藉由使溶劑組成物包含作為聚酯之良溶劑之1,3-二氧雜環戊烷與作為黏接劑發揮功能之聚酯之雙方，可彌補各個上述缺點，即便於已高速化之造管步驟中，或者即便是使用較多的作為PET瓶再利用原料之主原料之聚對苯二甲酸乙二酯原料之熱收縮性聚酯系膜，亦可穩定地顯現高剝離強度。 That is, by making the solvent composition contain both 1,3-dioxolane, which is a good solvent for polyester, and polyester, which functions as a binder, it is possible to make up for each of the above-mentioned disadvantages, even if high-speed In the process of chemical pipe making, or even the heat-shrinkable polyester film of polyethylene terephthalate, which is the main raw material of PET bottle recycling raw material, can stably exhibit high peel strength. .

另一方面，THF雖於聚酯之溶解性方面較1,3-二氧雜環戊烷差，但可使聚酯系膜溶解，從而溶劑黏接部具有適度的剝離強度。而且，較1,3二氧雜環戊烷亦不易產生溶劑穿透，因而適合於薄壁膜或使用了非晶性高之原料之熱收縮聚酯系膜。然而，若THF之塗佈量較少，則會產生剝離強度不足。 On the other hand, although THF is inferior to 1,3-dioxolane in the solubility of polyester, it can dissolve the polyester film, so that the solvent-bonded part has moderate peel strength. Moreover, compared with 1,3-dioxolane, it is not easy to generate solvent penetration, so it is suitable for thin-walled films or heat-shrinkable polyester films using raw materials with high amorphous properties. However, if the coating amount of THF is small, insufficient peel strength will occur.

而且，藉由如上述般使聚酯含有能夠成為非晶質成分之1種以上之單體成分，或者藉由進一步進行加熱而容易相對於THF溶解，因而可較佳地用作黏接劑，即便如上 述般THF之塗佈量減少，亦可獲得高剝離強度。進而，若如上述般利用熱使聚酯熔解而用作熱熔劑，則會發生不良情況。 In addition, as described above, the polyester can be preferably used as an adhesive by containing one or more monomer components that can become an amorphous component, or by further heating, so as to be easily dissolved in THF, Even if the coating amount of THF is reduced as described above, high peel strength can be obtained. Furthermore, as described above, when polyester is melted by heat and used as a hot melt, a problem will occur.

亦即，藉由使溶劑組成物包含作為聚酯之良溶劑之THF與作為黏接劑發揮功能之聚酯之雙方，可彌補各個上述缺點，即便於已高速化之造管步驟中，亦能夠穩定地顯現高剝離強度。而且，即便是非晶性較高之經薄壁化之熱收縮性聚酯系膜，亦不易產生溶劑穿透。 That is, by making the solvent composition contain both THF, which is a good solvent for polyester, and polyester, which functions as a binder, each of the above-mentioned disadvantages can be compensated, and even in the pipe-making process that has been accelerated, it is possible to Stable development of high peel strength. Moreover, even the thin-walled heat-shrinkable polyester-based film with high amorphousness is not prone to solvent penetration.

本發明之溶劑組成物中，除1,3-二氧雜環戊烷及/或THF與聚酯之外，亦可混合與1,3-二氧雜環戊烷及/或THF相溶之有機溶劑。與1,3-二氧雜環戊烷及/或THF相溶之有機溶劑中亦可使用聚酯之良溶劑或不良溶劑中之任一者。關於聚酯之良溶劑，可列舉1,4-二噁烷、四氫呋喃、1,2,2,2-四氯乙烷、苯、甲苯、二甲苯等。關於聚酯之不良溶劑，可列舉丙酮、甲基乙基酮、乙酸乙酯、乙酸丁酯、乙酸丙酯等。藉由於溶劑組成物中混合聚酯之不良溶劑，亦可防止溶劑穿透。然而，同樣地作為聚酯之不良溶劑之甲醇或乙醇等醇類及水由於會使溶劑組成物中所含之聚酯之溶解性顯著降低，故理想的是不與溶劑組成物混合。該等與1,3-二氧雜環戊烷及/或THF相溶之有機溶劑亦可單獨地使用或2種以上與溶劑組成物混合使用，相對於1,3-二氧雜環戊烷及/或THF100質量份，較佳為0質量份至300質量份，更佳為0質量份至200質量份，進而較佳為0質量份至100質量份。 In the solvent composition of the present invention, in addition to 1,3-dioxolane and/or THF and polyester, a solvent compatible with 1,3-dioxolane and/or THF can also be mixed Organic solvents. In the organic solvent compatible with 1,3-dioxolane and/or THF, either a good solvent or a poor solvent for polyester can be used. As a good solvent for polyester, 1,4-dioxane, tetrahydrofuran, 1,2,2,2-tetrachloroethane, benzene, toluene, xylene, etc. are mentioned. As a poor solvent of polyester, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, propyl acetate, etc. are mentioned. Solvent penetration can also be prevented by mixing the poor solvent of polyester in the solvent composition. However, alcohols such as methanol or ethanol and water, which are also poor solvents for polyester, significantly reduce the solubility of the polyester contained in the solvent composition, so it is desirable not to mix with the solvent composition. These organic solvents that are compatible with 1,3-dioxolane and/or THF can also be used alone or in combination with a solvent composition of two or more. And/or 100 parts by mass of THF, preferably 0 to 300 parts by mass, more preferably 0 to 200 parts by mass, still more preferably 0 to 100 parts by mass.

本發明之溶劑組成物中使用之聚酯亦可設為以對苯二甲酸乙二酯單元為主的構成成分。此處，「以對苯二甲酸乙二酯單元為主的構成成分」表示相對於聚酯之總構成成分量，含有50莫耳%以上之對苯二甲酸乙二酯單元。然而，由於耐化學品性增強，對1,3-二氧雜環戊烷或THF等有機溶劑之可溶性降低，故對苯二甲酸乙二酯單元於聚酯之構成單元100莫耳%中，較佳為70莫耳%以下，更佳為60莫耳%以下。而且，對苯二甲酸乙二酯單元於聚酯之構成單元100莫耳%中，較佳為5莫耳%以上，更佳為10莫耳%以上。 The polyester used in the solvent composition of the present invention may be a constituent mainly composed of ethylene terephthalate units. Here, "the constituents mainly composed of ethylene terephthalate units" means that 50 mol% or more of ethylene terephthalate units are contained with respect to the total constituent amount of the polyester. However, due to enhanced chemical resistance and reduced solubility in organic solvents such as 1,3-dioxolane or THF, ethylene terephthalate unit in 100 mol% of the constituent unit of polyester, Preferably it is 70 mol% or less, More preferably, it is 60 mol% or less. Furthermore, the ethylene terephthalate unit is preferably 5 mol % or more, and more preferably 10 mol % or more in 100 mol % of the constituent units of the polyester.

作為構成本發明之溶劑組成物中使用之聚酯之對苯二甲酸以外的其他二羧酸成分，可列舉間苯二甲酸、萘二甲酸、鄰苯二甲酸等芳香族二羧酸、己二酸、壬二酸、癸二酸、癸烷二甲酸等脂肪族二羧酸及脂環式二羧酸等。 As other dicarboxylic acid components other than terephthalic acid constituting the polyester used in the solvent composition of the present invention, aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, and phthalic acid, aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, and decanedicarboxylic acid, alicyclic dicarboxylic acids, and the like.

作為構成溶劑組成物中使用之聚酯之乙二醇以外的其他二醇成分，可列舉1,3-丙二醇、1,4-丁二醇、新戊二醇、己二醇等脂肪族二醇、1,4-環己烷二甲醇等脂環式二醇、雙酚A等芳香族系二醇等。 Aliphatic diols, such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and hexanediol, are mentioned as other diol components other than ethylene glycol constituting the polyester used in the solvent composition. , Alicyclic diols such as 1,4-cyclohexanedimethanol, aromatic diols such as bisphenol A, and the like.

本發明之溶劑組成物中使用之聚酯較佳為如下聚酯，即，含有間苯二甲酸等芳香族二羧酸或已二酸等脂肪族二羧酸、1,4-環己烷二甲醇等環狀二醇或具有3個以上碳數之二醇(例如1,3-丙二醇、1,4-丁二醇、新戊二醇、己二醇等)中之1種以上，且玻璃轉移點(Tg)設為70℃以下。 The polyester used in the solvent composition of the present invention is preferably a polyester containing an aromatic dicarboxylic acid such as isophthalic acid, an aliphatic dicarboxylic acid such as adipic acid, and 1,4-cyclohexanedicarboxylic acid. One or more of cyclic diols such as methanol or diols having 3 or more carbon atoms (such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol, hexanediol, etc.), and glass The transition point (Tg) was made 70°C or lower.

而且，溶劑組成物中使用之聚酯中，全聚酯樹脂中之 多元羧酸成分100莫耳%中或者多元醇成分100莫耳%中的可能成為非晶質成分之1種以上之單體成分之合計為30莫耳%以上，較佳為40莫耳%以上，更佳為50莫耳%以上。其原因在於，若可能成為非晶質成分之單體成分之合計小於30莫耳%，則對以1,3-二氧雜環戊烷為首之有機溶劑之溶解性降低，從而無法用作溶劑。 In addition, in the polyester used in the solvent composition, one or more monomers that may be amorphous components in 100 mol% of the polycarboxylic acid component or 100 mol% of the polyol component in the total polyester resin The total of the components is 30 mol% or more, preferably 40 mol% or more, more preferably 50 mol% or more. The reason for this is that if the total of the monomer components that may become amorphous components is less than 30 mol %, the solubility in organic solvents including 1,3-dioxolane will decrease, and it cannot be used as a solvent. .

關於可能成為非晶質成分之單體，例如可列舉間苯二甲酸、鄰苯二甲酸、己二酸、癸二酸、1,4-環己烷二甲醇、新戊二醇、1,3-丙二醇、1,4-丁二醇、己二醇。 Examples of monomers that may become amorphous components include isophthalic acid, phthalic acid, adipic acid, sebacic acid, 1,4-cyclohexanedimethanol, neopentyl glycol, 1,3 - Propylene glycol, 1,4-butanediol, hexanediol.

本發明之溶劑組成物中所含之聚酯之含量之上限較佳為40質量%以下，更佳為34質量%以下，進而較佳為25質量%以下，尤佳為20質量%以下。其原因在於，溶劑組成物中所含之聚酯之含量越多則溶劑組成物之黏度越高，於已高速化之造管步驟中，難以穩定地將溶劑組成物以固定量塗佈於聚酯系膜。而且，溶劑組成物中所含之聚酯之含量之下限較佳為1質量%以上，更佳為2質量%以上，進而較佳為5質量%以上，尤佳為8質量%以上。若溶劑組成物中所含之聚酯之含量過低，則於將含有多於25質量%的聚對苯二甲酸乙二酯之聚酯系膜黏接時，無法獲得充分之剝離強度，而且，溶劑組成物之塗佈量減少之情形時黏接部之剝離強度不足。 The upper limit of the content of the polyester contained in the solvent composition of the present invention is preferably 40% by mass or less, more preferably 34% by mass or less, still more preferably 25% by mass or less, particularly preferably 20% by mass or less. The reason is that the higher the content of polyester contained in the solvent composition, the higher the viscosity of the solvent composition, and it is difficult to stably apply the solvent composition to the polymer at a fixed amount in the pipe-making process that has been accelerated. Ester film. Furthermore, the lower limit of the content of the polyester contained in the solvent composition is preferably 1 mass % or more, more preferably 2 mass % or more, still more preferably 5 mass % or more, and particularly preferably 8 mass % or more. If the content of the polyester contained in the solvent composition is too low, sufficient peel strength cannot be obtained when a polyester-based film containing more than 25% by mass of polyethylene terephthalate is bonded, and the , When the coating amount of the solvent composition is reduced, the peel strength of the adhesive part is insufficient.

亦可視需要向本發明之溶劑組成物中添加各種添加劑或減黏劑、熱穩定劑、著色用顏料、防著色劑、紫外線吸收劑等。 Various additives or viscosity reducing agents, heat stabilizers, coloring pigments, anti-coloring agents, ultraviolet absorbers, etc. can also be added to the solvent composition of the present invention as required.

而且，溶劑組成物之黏度之下限雖未作特別限定，但若黏度過高，則於已高速化之造管步驟中難以穩定地塗佈固定量，因而較佳為小於100mPa‧s，更佳為90mPa‧s以下，進而較佳為80mPa‧s以下，尤佳為70mPa‧s以下。 In addition, although the lower limit of the viscosity of the solvent composition is not particularly limited, if the viscosity is too high, it will be difficult to stably coat a fixed amount during the high-speed pipe-making process, so it is preferably less than 100 mPa·s, more preferably It is 90 mPa·s or less, more preferably 80 mPa·s or less, and particularly preferably 70 mPa·s or less.

造管步驟時，較佳為使用公知之中封機(center seal machine)等對熱收縮性聚酯系膜以50mg/m2至550mg/m2程度塗佈溶劑組成物。而且，為了抑制黏接部之剝離，造管步驟中之溶劑組成物之塗佈寬度較佳為1mm以上，上限雖未作特別限定，但由於所使用之標籤面積越小則成本越少，故較佳為10mm以下。 In the pipe-making step, it is preferable to apply the solvent composition to the heat-shrinkable polyester film at about 50 mg/m 2 to 550 mg/m 2 using a known center seal machine or the like. In addition, in order to suppress the peeling of the adhesive part, the coating width of the solvent composition in the pipe making step is preferably 1 mm or more. Although the upper limit is not particularly limited, the smaller the label area used, the lower the cost. Therefore, Preferably it is 10 mm or less.

造管步驟之速度雖未作特別限定，就高速化方面而言較佳為300m/分鐘至500m/分鐘。造管步驟後之管狀標籤通常被平坦地捲起且呈卷狀捲繞後，捲出標籤並以預定長度裁斷，而形成最終製品，亦可於造管步驟後，不捲繞為卷而進行裁斷步驟。 Although the speed of the pipe-making step is not particularly limited, it is preferably 300 m/min to 500 m/min in terms of high speed. After the pipe making step, the tubular label is usually rolled flat and rolled in a roll shape, then the label is rolled out and cut to a predetermined length to form the final product. cutting step.

本發明之熱收縮性聚酯系標籤中，溶劑黏接部之剝離強度為2N/15mm以上，較佳為3N/15mm以上，更佳為4N/15mm以上。若剝離強度為2N/15mm以上，則可防止使用中剝離等麻煩。而且，溶劑黏接部之對離強度之上限小於15N/15mm。其原因在於，剝離強度雖然越高越佳，但本發明中難以實現15N/15mm以上之剝離強度。剝離強度之測定方法依據實施例所記載之方法。 In the heat-shrinkable polyester label of the present invention, the peel strength of the solvent-bonded portion is 2N/15mm or more, preferably 3N/15mm or more, more preferably 4N/15mm or more. When the peel strength is 2N/15mm or more, troubles such as peeling during use can be prevented. Moreover, the upper limit of the separation strength of the solvent-bonded portion is less than 15N/15mm. The reason for this is that, although the higher the peel strength, the better, it is difficult to achieve a peel strength of 15 N/15 mm or more in the present invention. The measurement method of peeling strength is based on the method described in the Example.

構成本發明之熱收縮性聚酯系標籤之熱收縮性聚酯 系膜的厚度較佳為5μm以上60μm以下，更佳為8μm以上45μm以下。就標籤薄壁化之觀點而言，更佳為30μm以下。亦可於該標籤中之黏接部以外的部分設置印刷層。 The thickness of the heat-shrinkable polyester film constituting the heat-shrinkable polyester label of the present invention is preferably 5 m or more and 60 m or less, more preferably 8 m or more and 45 m or less. From the viewpoint of making the label thinner, it is more preferably 30 μm or less. A printed layer can also be provided on the part other than the adhesive part in the label.

本發明之熱收縮性聚酯系標籤中，90℃之熱水中10秒之熱收縮率較佳為於主收縮方向上為40%以上。若熱收縮率為40%以上，則可獲得美麗之收縮完成性。若小於40%，則熱收縮力不足，當被覆於容器等而收縮時，因不密接於容器而發生外觀不良，故欠佳。於與主收縮方向正交之方向上，90℃之熱水中之熱收縮率較佳為15%以下。若超過15%，則因容易引起被稱作標籤縱向收縮之縱向收縮(longitudinal shrink)之現象，故欠佳。另外，主收縮方向之熱收縮率係指試樣之收縮最多之方向上的熱收縮率之含義，主收縮方向由正方形之試樣之縱向或橫向之長度而決定。熱收縮率(%)之測定方法依據實施例所記載之方法。 In the heat-shrinkable polyester label of the present invention, the heat shrinkage rate in hot water at 90° C. for 10 seconds is preferably 40% or more in the main shrinkage direction. When the thermal shrinkage rate is 40% or more, beautiful shrinkage completion can be obtained. If it is less than 40%, the thermal shrinkage force is insufficient, and when it is coated on a container or the like and shrinks, it is not preferable because it does not adhere to the container and causes poor appearance. In the direction orthogonal to the main shrinkage direction, the thermal shrinkage rate in hot water at 90°C is preferably 15% or less. If it exceeds 15%, a phenomenon called longitudinal shrinkage (longitudinal shrink) called longitudinal shrinkage of the label is likely to occur, so it is not preferable. In addition, the thermal shrinkage rate in the main shrinkage direction refers to the meaning of the thermal shrinkage rate in the direction in which the sample shrinks the most, and the main shrinkage direction is determined by the longitudinal or transverse length of the square sample. The measurement method of the thermal shrinkage rate (%) is based on the method described in the Examples.

本發明之熱收縮性聚酯系標籤中使用之聚酯較佳設為以對苯二甲酸乙二酯單元為主的構成成分。其原因在於這樣強度或耐熱性優異。對苯二甲酸乙二酯單元於聚酯之構成單元100莫耳%中，較佳為50莫耳%以上，更佳為60莫耳%以上。 The polyester used for the heat-shrinkable polyester label of the present invention is preferably a constituent mainly composed of ethylene terephthalate units. The reason for this is that such strength and heat resistance are excellent. The ethylene terephthalate unit is preferably 50 mol % or more, more preferably 60 mol % or more in 100 mol % of the constituent units of the polyester.

對苯二甲酸乙二酯單元亦可包含來自PET瓶再利用原料之單元。PET瓶再利用原料係將飲料用之PET瓶加工成薄片(flake)或顆粒(pellet)者。當將聚酯系膜製膜時，較佳為於聚酯原料100質量%中，於90質量%以下使用該 PET瓶再利用原料。若使用超過90質量%的PET瓶再利用原料，則由於構成PET瓶之聚對苯二甲酸乙二酯之結晶性高，故有所獲得之膜之熱收縮特性降低之虞。為了促進再利用，理想的是於聚酯原料100質量%中，使用20質量%以上的PET瓶再利用原料。 The ethylene terephthalate unit may also include units from PET bottle reuse feedstock. PET bottle recycling raw materials are those that process PET bottles for beverages into flakes or pellets. When the polyester-based film is formed into a film, it is preferable to use the PET bottle recycling raw material in an amount of 90 mass % or less in 100 mass % of the polyester raw material. If more than 90 mass % of the PET bottle is used as a recycled raw material, since the crystallinity of polyethylene terephthalate constituting the PET bottle is high, the thermal shrinkage characteristics of the obtained film may be lowered. In order to promote recycling, it is desirable to use 20 mass % or more of PET bottle recycling raw materials in 100 mass % of polyester raw materials.

作為構成本發明之熱收縮性聚酯系膜中使用之聚酯之對苯二甲酸以外的其他二羧酸成分，可列舉間苯二甲酸、2,6-萘二甲酸、鄰苯二甲酸等芳香族二羧酸、己二酸、壬二酸、癸二酸、癸烷二甲酸等脂肪族二羧酸及1,4-環己烷二甲酸等脂環式二羧酸等。 As other dicarboxylic acid components other than terephthalic acid constituting the polyester used for the heat-shrinkable polyester film of the present invention, isophthalic acid, 2,6-naphthalenedicarboxylic acid, phthalic acid, etc. may be mentioned Alicyclic dicarboxylic acids such as aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and the like.

於使聚酯中含有脂肪族二羧酸(例如己二酸、癸二酸、癸烷二甲酸等)之情形時，含有率較佳為小於3莫耳%(二羧酸成分100莫耳%中)。使用含有3莫耳%以上之該等脂肪族二羧酸之聚酯所獲得之熱收縮性聚酯系標籤中，高速安裝時之膜黏性容易不充分。 When the polyester contains aliphatic dicarboxylic acids (such as adipic acid, sebacic acid, decanedicarboxylic acid, etc.), the content is preferably less than 3 mol% (dicarboxylic acid component 100 mol%) middle). In the heat-shrinkable polyester-based label obtained by using the polyester containing these aliphatic dicarboxylic acids in an amount of 3 mol% or more, the film adhesion during high-speed installation tends to be insufficient.

而且，較佳為不含有三元以上之多元羧酸(例如偏苯三甲酸、均苯四甲酸及該等之酐等)。使用含有該等多元羧酸之聚酯而獲得之熱收縮性聚酯系標籤難以達成所需之高收縮率。 Moreover, it is preferable not to contain the polyvalent carboxylic acid (for example, trimellitic acid, pyromellitic acid, these anhydrides, etc.) of trivalent or more. The heat-shrinkable polyester-based labels obtained by using polyesters containing these polycarboxylic acids are difficult to achieve a desired high shrinkage rate.

作為構成本發明之熱收縮性聚酯系膜中使用之聚酯之乙二醇以外的二醇成分，可列舉1,3-丙二醇、1,4-丁二醇、新戊二醇、己二醇等脂肪族二醇、1,4-環己烷二甲醇等脂環式二醇、雙酚A等芳香族系二醇等。 Examples of diol components other than ethylene glycol constituting the polyester used in the heat-shrinkable polyester film of the present invention include 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and hexanediol. Aliphatic diols such as alcohols, alicyclic diols such as 1,4-cyclohexanedimethanol, aromatic diols such as bisphenol A, and the like.

本發明之熱收縮性聚酯系膜中使用之聚酯較佳為如 下聚酯，即，含有1,4-環己烷二甲醇等環狀二醇、或具有3至6個碳數之二醇(例如1,3-丙二醇、1,4-丁二醇、新戊二醇、己二醇等)中之1種以上，且玻璃轉移點(Tg)調整為60℃至80℃。 The polyester used in the heat-shrinkable polyester film of the present invention is preferably a polyester containing a cyclic diol such as 1,4-cyclohexanedimethanol, or having 3 to 6 carbon atoms One or more of alcohols (for example, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, hexanediol, etc.), and the glass transition point (Tg) is adjusted to 60°C to 80°C.

而且，本發明之熱收縮性聚酯系膜中使用之聚酯中，於全聚酯樹脂中之多元醇成分100莫耳%中或者多元羧酸成分100莫耳%中的可能成為非晶質成分之1種以上之單體成分之合計為15莫耳%以上，較佳為16莫耳%以上，更佳為17莫耳%以上，尤佳為18莫耳%以上。可能成為非晶質成分之單體成分之合計之上限雖未作特別限定，但較佳為30莫耳%。 Furthermore, in the polyester used in the heat-shrinkable polyester film of the present invention, the polyol component in 100 mol % or the polyvalent carboxylic acid component in 100 mol % in the all-polyester resin may become amorphous. The total of one or more monomer components of the components is 15 mol % or more, preferably 16 mol % or more, more preferably 17 mol % or more, and still more preferably 18 mol % or more. Although the upper limit of the sum total of the monomer components which may become an amorphous component is not specifically limited, 30 mol% is preferable.

關於可能成為非晶質成分之單體，例如可列舉新戊二醇、1,4-環己烷二甲醇、間苯二甲酸、1,4-環己烷二甲酸、2,6-萘二甲酸、2,2-二乙基-1,3-丙二醇、2-正丁基-2-乙基-1,3-丙二醇、2,2-異丙基-1,3-丙二醇、2,2-二正丁基-1,3-丙二醇、己二醇。該等之中，較佳為使用新戊二醇、1,4-環己烷二甲醇或間苯二甲酸。 Examples of monomers that may become amorphous components include neopentyl glycol, 1,4-cyclohexanedimethanol, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 2,6-naphthalenedi Formic acid, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2 -Di-n-butyl-1,3-propanediol, hexanediol. Among these, neopentyl glycol, 1,4-cyclohexanedimethanol, or isophthalic acid is preferably used.

此處，將對上述「可能成為非晶質成分之」這一用語之解釋進行詳細說明。 Here, the explanation of the term "possible to become an amorphous component" will be explained in detail.

本發明中，「非晶性聚合物」具體而言是指DSC(differential scanning calorimeter；示差掃描熱量分析裝置)中之測定中不具有熔解所引起之吸熱峰值之情形。非晶性聚合物是指結晶化未得到實質進展而無法獲得結 晶狀態、或者即便結晶化而結晶化度亦極低者。 In the present invention, "amorphous polymer" specifically refers to a case in which there is no endothermic peak due to melting in measurement by DSC (differential scanning calorimeter; differential scanning calorimeter). An amorphous polymer refers to a polymer that does not substantially progress to crystallization and cannot obtain a crystalline state, or that has an extremely low degree of crystallinity even if it is crystallized.

而且，本發明中「結晶性聚合物」是指並非為上述「非晶性聚合物」者，亦即，DSC示差掃描熱量分析裝置中之測定中具有熔解所引起之吸熱峰值之情形。結晶性聚合物是指具有若聚合物升溫則可結晶化之能夠結晶化之性質或者已結晶化者。 In addition, the "crystalline polymer" in the present invention refers to a case other than the above-mentioned "amorphous polymer", that is, a case where there is an endothermic peak due to melting in the measurement by a DSC differential scanning calorimeter. The crystalline polymer refers to a polymer having the property of being able to be crystallized or being crystallized by being crystallized when the temperature of the polymer is increased.

一般而言，關於單體單元多個結合而成之狀態的聚合物，於具有聚合物之立體規則性低、聚合物之對象性差、聚合物之側鏈大、聚合物之分枝多、聚合物彼此之分子間凝聚力小等諸條件之情形時，會成為非晶性聚合物。然而，亦有如下情形：根據存在狀態，結晶化充分進行從而成為結晶性聚合物。例如，即便是側鏈大之聚合物，於聚合物由單一單體單元構成之情形時，結晶化充分進行而可成為結晶性。因此，即便是同一單體單元，聚合物有時為結晶性，亦有時為非晶性，因而本發明中使用「可能成為非晶質成分之」這一表達。 Generally speaking, for a polymer in a state where a plurality of monomer units are combined, the three-dimensional regularity of the polymer is low, the object property of the polymer is poor, the side chain of the polymer is large, the branching of the polymer is many, and the polymerization When the intermolecular cohesion between substances is small and other conditions, it will become an amorphous polymer. However, depending on the state of existence, crystallization progresses sufficiently to become a crystalline polymer. For example, even in a polymer with a large side chain, when the polymer is composed of a single monomer unit, crystallization progresses sufficiently to become crystalline. Therefore, even if it is the same monomer unit, the polymer may be crystalline and may be amorphous, and thus the expression "possible to become an amorphous component" is used in the present invention.

此處，本發明中，單體單元是指由一個多元醇分子及一個多元羧酸分子衍生之構成聚合物之重複單元。 Here, in the present invention, the monomer unit refers to a repeating unit that constitutes a polymer derived from one polyol molecule and one polycarboxylic acid molecule.

於由對苯二甲酸及乙二醇構成之單體單元(對苯二甲酸乙二酯單元)為構成聚合物的主要之單體單元之情形時，可列舉由間苯二甲酸與乙二醇構成之單體單元、由對苯二甲酸與新戊二醇構成之單體單元、由對苯二甲酸與 1,4-環己烷二甲醇構成之單體單元、由間苯二甲酸與丁二醇構成之單體單元等，作為來自上述可能成為非晶質成分之單體的單元。 When the monomeric unit (ethylene terephthalate unit) composed of terephthalic acid and ethylene glycol is the main monomeric unit constituting the polymer, the monomeric unit composed of isophthalic acid and ethylene glycol may be mentioned. Monomer unit composed of terephthalic acid and neopentyl glycol Monomer unit composed of terephthalic acid and 1,4-cyclohexanedimethanol Monomer unit composed of isophthalic acid and butylene The monomer unit etc. which comprise a diol are a unit derived from the monomer which may become an amorphous component mentioned above.

而且，較佳為不含有碳數8個以上之二醇(例如辛二醇等)或三元以上之多元醇(例如三羥甲基丙烷、三羥甲基乙烷、甘油、雙甘油等)。使用含有該等二醇或多元醇之聚酯而獲得之熱收縮性聚酯系標籤中，難以達成所需之高收縮率。而且，較佳為亦盡可能地不含有二乙二醇、三乙二醇、聚乙二醇。 Furthermore, it is preferable not to contain diols having 8 or more carbon atoms (eg, caprylyl glycol, etc.) or polyhydric alcohols having 3 or more valences (eg, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.) . In a heat-shrinkable polyester-based label obtained by using a polyester containing these diols or polyols, it is difficult to achieve a desired high shrinkage rate. Moreover, it is also preferable not to contain diethylene glycol, triethylene glycol, and polyethylene glycol as much as possible.

而且，聚酯中，較佳為全聚酯樹脂中之多元醇成分100莫耳%中及多元羧酸成分100莫耳%中(亦即合計200莫耳%中)的非晶成分共聚合。藉由進行共聚合而無原料偏析之擔憂，能夠防止膜原料組成變動所引起之膜物性之變化。進而，藉由進行共聚合而促進酯交換，藉此非晶量增加從而對提高主收縮方向之收縮率有利。 In addition, in the polyester, it is preferable to copolymerize the amorphous components in 100 mol % of the polyol component and 100 mol % of the polyvalent carboxylic acid component in the total polyester resin (that is, in a total of 200 mol %). By performing the copolymerization without fear of segregation of raw materials, it is possible to prevent changes in film properties due to changes in the composition of film raw materials. Furthermore, it is advantageous to increase the shrinkage rate in the main shrinkage direction by promoting the transesterification by copolymerizing and increasing the amount of amorphous.

可視需要向形成本發明之標籤中使用之熱收縮性聚酯系膜的樹脂中添加各種添加劑，例如蠟類、抗氧化劑、抗靜電劑、結晶成核劑、減黏劑、熱穩定劑、著色用顏料、防著色劑、紫外線吸收劑等。 Various additives, such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers, colorants, may be added to the resin forming the heat-shrinkable polyester film used in the label of the present invention as required. Use pigments, anti-colorants, UV absorbers, etc.

向形成上述熱收縮性聚酯系膜之樹脂中添加作為使膜之作業性(滑動性)變得良好之潤滑劑的微粒子對於使造管步驟高速化而言較佳。可選擇任意者作為微粒子，例如，作為無機系微粒子，可列舉二氧化矽、氧化鋁、二氧化鈦、碳酸鈣、高嶺土、硫酸鋇等，作為有機系微粒子， 例如可列舉丙烯酸系樹脂粒子、三聚氰胺樹脂粒子、矽酮樹脂粒子、交聯聚苯乙烯粒子等。微粒子之平均粒徑可視需要於0.05μm至3.0μm之範圍內(已由庫爾特計數器測定之情形時)適當選擇。 It is preferable to add microparticles|fine-particles as a lubricant which improves the workability|operativity (sliding property) of a film to the resin which forms the said heat-shrinkable polyester-type film in order to speed up a pipe-making process. Any one can be selected as the fine particles, for example, inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, etc., and organic fine particles include acrylic resin particles and melamine resin particles, for example , silicone resin particles, cross-linked polystyrene particles, etc. The average particle diameter of the microparticles may be appropriately selected within the range of 0.05 μm to 3.0 μm (when measured by a Coulter counter) as needed.

作為於形成熱收縮性聚酯系膜之樹脂中調配上述粒子之方法，例如可於製造聚酯之任意階段添加，但較佳為於酯化之階段或者酯交換反應結束後縮聚反應開始前之階段，作為分散於乙二醇等之漿料而添加以促進縮聚反應。而且，較佳為藉由如下方法等進行，即，使用附通氣孔(vent)之混練擠出機而將分散於乙二醇或水等之粒子之漿料與聚酯原料進行摻合之方法，或者使用混練擠出機將經乾燥之粒子與聚酯原料摻合之方法。 As a method for preparing the above-mentioned particles in the resin for forming the heat-shrinkable polyester film, for example, it can be added at any stage of polyester production, but it is preferably at the stage of esterification or before the start of the polycondensation reaction after the end of the transesterification reaction. In the first stage, it is added as a slurry dispersed in ethylene glycol or the like to promote the polycondensation reaction. Furthermore, it is preferable to carry out a method of blending a polyester raw material with a slurry of particles dispersed in ethylene glycol, water, etc., using a kneading extruder with a vent. , or use a mixing extruder to blend the dried particles with polyester raw materials.

為了使膜表面之印刷性或黏接性良好，亦可對上述熱收縮性聚酯系膜實施電暈處理、塗覆處理或火焰處理等。 In order to make the printability and adhesiveness of the film surface good, the above-mentioned heat-shrinkable polyester film may be subjected to corona treatment, coating treatment, flame treatment, or the like.

另外，本發明之熱收縮性聚酯系膜中亦可包含至少具有1層聚酯樹脂層之積層型聚酯膜。當聚酯樹脂層積層2層以上時，該聚酯樹脂層可為相同組成之聚酯，亦可為不同組成之聚酯。而且，作為其他層之能夠積層之層，只要是熱塑性樹脂層，則不作特別限定，自價格或熱收縮特性考慮，較佳為聚苯乙烯系樹脂層。 Moreover, the heat-shrinkable polyester film of this invention may contain the laminated polyester film which has at least 1 layer of polyester resin layers. When two or more polyester resin layers are laminated, the polyester resin layers may be polyesters of the same composition or polyesters of different compositions. Moreover, as a layer which can be laminated|stacked among other layers, as long as it is a thermoplastic resin layer, it will not specifically limit, From a viewpoint of price and thermal shrinkage characteristics, a polystyrene resin layer is preferable.

較佳為向聚苯乙烯系樹脂中添加熱塑性樹脂及/或橡膠成分。作為熱塑性樹脂，可列舉具有雜排結構(atactic structure)之聚苯乙烯、AS樹脂、ABS樹脂等苯乙烯系樹 脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂、尼龍6、尼龍66、尼龍12、尼龍4、聚己二醯己二胺等聚醯胺系樹脂、聚乙烯、聚丙烯、聚丁烯等聚烯烴系樹脂等。 It is preferable to add a thermoplastic resin and/or a rubber component to the polystyrene resin. Examples of the thermoplastic resin include polystyrene having an atactic structure, styrene-based resins such as AS resin and ABS resin, polyethylene terephthalate, polyethylene naphthalate, and polyethylene terephthalate. Polyester resins such as butylene dicarboxylate, polyamide resins such as nylon 6, nylon 66, nylon 12, nylon 4, and polyhexamethylene diamine, polyolefin resins such as polyethylene, polypropylene, and polybutene resin, etc.

另一方面，作為橡膠成分，較佳為含有苯乙烯系化合物作為其構成成分之橡膠狀共聚物，可列舉自苯乙烯與橡膠成分中分別選擇一種以上共聚合而成之無規、嵌段或接枝共聚物。作為此種橡膠狀共聚物，例如可列舉苯乙烯-丁二烯共聚物橡膠、苯乙烯-異戊二烯嵌段共聚物、該等丁二烯部分之一部分或者全部氫化而成之橡膠、丙烯酸甲酯-丁二烯-苯乙烯共聚物橡膠、丙烯腈-丁二烯-苯乙烯共聚物橡膠、丙烯腈-丙烯酸烷基酯-丁二烯-苯乙烯共聚物橡膠、甲基丙烯酸甲酯-丙烯酸烷基酯-丁二烯-苯乙烯共聚物橡膠等。含有上述苯乙烯系化合物作為其構成成分之橡膠狀共聚物因具有苯乙烯單元，故相對於具有對排結構(syndiotactic structure)之聚苯乙烯系樹脂之分散性良好，對聚苯乙烯系樹脂之可塑性改良效果較大。而且，作為相溶性調整劑，可較佳地使用含有上述苯乙烯系化合物作為其構成成分之橡膠狀共聚物。 On the other hand, as the rubber component, a rubber-like copolymer containing a styrene-based compound as its constituent is preferable, and examples include random, block or random copolymers obtained by copolymerizing one or more selected from styrene and rubber components, respectively. graft copolymer. Examples of such a rubbery copolymer include styrene-butadiene copolymer rubber, styrene-isoprene block copolymer, rubber obtained by hydrogenating a part or all of these butadiene parts, and acrylic acid. Methyl-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber, methyl methacrylate- Alkyl acrylate-butadiene-styrene copolymer rubber, etc. Since the rubber-like copolymer containing the above-mentioned styrene-based compound as its constituent has styrene units, it has good dispersibility with respect to the polystyrene-based resin having a syndiotactic structure. The plasticity improvement effect is large. Further, as the compatibility modifier, a rubber-like copolymer containing the above-mentioned styrene-based compound as its constituent can be preferably used.

另一方面，作為前述橡膠成分，此外可使用天然橡膠、聚丁二烯、聚異戊二烯、聚異丁烯、氯丁烯、乙烯-丙烯共聚物橡膠、胺基甲酸酯橡膠、矽酮橡膠、丙烯酸系橡膠、聚醚-酯橡膠、聚酯-酯橡膠等。 On the other hand, as the aforementioned rubber component, natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene, ethylene-propylene copolymer rubber, urethane rubber, and silicone rubber can also be used. , acrylic rubber, polyether-ester rubber, polyester-ester rubber, etc.

而且，聚苯乙烯系樹脂之重量平均分子量較佳為 10,000以上，更佳為50,000以上。重量平均分子量小於10,000者因膜之強伸度特性或耐熱性容易降低，故欠佳。重量平均分子量之上限雖未作特別限定，但由於會發生如下情況，故欠佳，即，若重量平均分子量高於1,500,000，則會伴隨延伸張力之增大而發生斷裂。 Furthermore, the weight average molecular weight of the polystyrene resin is preferably 10,000 or more, more preferably 50,000 or more. Those with a weight-average molecular weight of less than 10,000 are not preferable because the tensile properties and heat resistance of the film tend to decrease. The upper limit of the weight-average molecular weight is not particularly limited, but it is unfavorable because when the weight-average molecular weight exceeds 1,500,000, breakage occurs with an increase in the stretching tension.

聚苯乙烯系樹脂已由各種廠商市售有各種等級者，亦可使用市售者。其他層可為1層亦可為2層以上。 Polystyrene-based resins are commercially available in various grades from various manufacturers, and commercially available ones can also be used. The other layers may be one layer or two or more layers.

本發明之熱收縮性聚酯系膜可藉由如下而獲得，即，利用擠出機將上述聚酯原料熔融擠出而形成未延伸膜，並藉由以下所示之預定之方法將該未延伸膜進行橫向單軸延伸或者縱橫雙軸延伸並進行熱處理。積層之情形時，使用多個擠出機或分流模頭(feed block)、多歧管即可。另外，聚酯可利用公知之方法使前述較佳之二羧酸成分與二醇成分縮聚而獲得。而且，通常係將碎片(tip)狀之聚酯混合2種以上而用作膜之原料。積層之情形時，使用多個擠出機即可。 The heat-shrinkable polyester film of the present invention can be obtained by melt-extruding the above polyester raw material with an extruder to form an unstretched film, and by a predetermined method shown below, the unstretched film can be obtained. The stretched film is subjected to lateral uniaxial stretching or longitudinal and lateral biaxial stretching and heat treatment. In the case of lamination, a plurality of extruders, feed blocks, and manifolds may be used. Moreover, polyester can be obtained by polycondensing the said preferable dicarboxylic acid component and a diol component by a well-known method. In addition, usually two or more types of polyesters in the form of a tip are mixed and used as a raw material of the film. In the case of lamination, a plurality of extruders may be used.

於將原料樹脂熔融擠出時，較佳為使用料斗乾燥機、槳葉乾燥機等乾燥機、或真空乾燥機使聚酯原料乾燥。如此使聚酯原料乾燥後，利用擠出機以200℃至300℃之溫度熔融而擠出為膜狀。擠出時，可採用T型模法、管式法等既有之任意方法。 When the raw resin is melt-extruded, the polyester raw material is preferably dried using a dryer such as a hopper dryer, a paddle dryer, or a vacuum dryer. After drying the polyester raw material in this way, it is melted at a temperature of 200°C to 300°C by an extruder and extruded into a film. When extruding, any existing methods such as T-die method and tubular method can be used.

然後，藉由將擠出後之片狀熔融樹脂急冷而可獲得未延伸膜。另外，作為將熔融樹脂急冷之方法，可較佳地採用如下方法，即，藉由將熔融樹脂自噴嘴澆鑄至轉筒上並 進行急冷固化而獲得實質未配向之樹脂片。 Then, an unstretched film can be obtained by quenching the extruded sheet-like molten resin. In addition, as a method of quenching the molten resin, a method of obtaining a substantially unaligned resin sheet by casting the molten resin onto a rotating drum from a nozzle and quenching and solidifying can be preferably employed.

所獲得之未延伸膜視需要利用輥以70℃至100℃，較佳為以80℃至90℃加熱後，使用輥之速度差而縱延伸至1.1倍至1.8倍。所獲得之縱延伸後之膜視需要以80℃至120℃，較佳為以90℃至110℃預熱，然後利用拉幅機等向橫向(相對於擠出方向正交之方向)延伸至3.0倍以上，較佳為3.5倍以上7倍以下。延伸溫度為65℃以上100℃以下，較佳為70℃以上95℃以下。 The obtained unstretched film is heated at 70°C to 100°C, preferably 80°C to 90°C, as necessary, and longitudinally stretched by 1.1 to 1.8 times using the speed difference of the rollers. The obtained longitudinally stretched film may be preheated at 80°C to 120°C, preferably at 90°C to 110°C, as needed, and then stretched in the transverse direction (direction perpendicular to the extrusion direction) using a tenter, etc. 3.0 times or more, preferably 3.5 times or more and 7 times or less. The stretching temperature is 65°C or higher and 100°C or lower, preferably 70°C or higher and 95°C or lower.

而且，較佳為橫向延伸後，以較延伸溫度高1℃至30℃之溫度進行熱處理。熱處理係為了緩和延伸後之膜之緊張狀態而進行，以熱處理時之溫度進行熱收縮率之調整，且對於減少自然收縮率亦有效果。由此，獲得本發明之熱收縮性聚酯系膜。 Furthermore, it is preferable to perform heat treatment at a temperature 1°C to 30°C higher than the stretching temperature after lateral stretching. The heat treatment is performed to relieve the tension of the stretched film, and the thermal shrinkage rate is adjusted at the temperature during the heat treatment, and it is also effective in reducing the natural shrinkage rate. Thereby, the heat-shrinkable polyester film of this invention was obtained.

本發明之熱收縮性聚酯系膜可藉由現有公知之方法標籤化。作為一例，對已裁斷為所期望之寬度之熱收縮性聚酯系膜實施適當之印刷，藉由前述溶劑組成物將膜之左右端部重合並接合而製造出管膜。將該管膜裁斷為適當之長度，從而形成管狀標籤。 The heat-shrinkable polyester film of the present invention can be labelled by a conventionally known method. As an example, appropriate printing is performed on a heat-shrinkable polyester film cut to a desired width, and the left and right ends of the film are superimposed and joined with the solvent composition to produce a tubular film. The tubular film is cut to an appropriate length to form a tubular label.

視需要藉由公知之方法於上述標籤形成穿孔後，被覆於PET瓶，使該PET瓶載置於帶式輸送機等而通過吹送蒸氣之類型的收縮隧道(蒸氣隧道)或吹送熱風之類型的收縮隧道(熱風隧道)之內部。藉由通過該等隧道時標籤熱收縮，而標籤被安裝於PET瓶等瓶容器。 If necessary, the label is perforated by a known method, and then it is covered with a PET bottle, and the PET bottle is placed on a belt conveyor or the like and passed through a steam-blowing type of shrink tunnel (steam tunnel) or a hot-air-blown type. Inside the shrink tunnel (hot air tunnel). The labels are attached to bottle containers such as PET bottles by heat shrinking the labels while passing through these tunnels.

本發明之包裝體較佳為由本發明之熱收縮性聚酯系 膜而獲得，較佳為具有穿孔或凹口之標籤係被覆於包裝對象物之至少外周之一部分且熱收縮而形成。關於包裝對象物，可列舉以飲料用之PET瓶為首的各種瓶、罐、糕點或盒飯等之塑膠容器、紙製之箱等。另外，通常於使由熱收縮性聚酯系膜獲得之標籤熱收縮而被覆於該等包裝對象物之情形時，使該標籤熱收縮約5%至70%左右而密接於包裝體。另外，可對被覆於包裝對象物之標籤實施印刷，亦可不實施印刷。 The package of the present invention is preferably obtained from the heat-shrinkable polyester film of the present invention, and preferably a label having perforations or notches is formed by covering at least a part of the outer periphery of an object to be packaged and heat-shrinking. The packaging object includes various bottles including PET bottles for beverages, cans, plastic containers such as confectionery and lunch boxes, and paper boxes. In addition, when the label obtained from the heat-shrinkable polyester film is generally thermally shrunk to cover the packaging objects, the label is thermally shrunk by about 5% to 70% to closely adhere to the package. In addition, printing may or may not be performed on the label to be coated on the object to be packaged.

[實施例] [Example]

以下，藉由實施例對本發明進行進一步詳細敘述，下述實施例並非限制本發明者，於不脫離本發明之主旨之範圍內變更實施之情形亦包含於本發明中。另外，實施例及比較例中獲得之膜之物性之測定方法為以下所示。 Hereinafter, the present invention will be further described in detail by way of examples, but the following examples are not intended to limit the present invention, and the present invention also includes changes and implementations within the scope of not departing from the gist of the present invention. In addition, the measurement method of the physical property of the film obtained in the Example and the comparative example is as follows.

[密度] [density]

根據JIS(Japanese Industrial Standards；日本工業標準)K7112，將膜浸漬於密度梯度液(硝酸鈣水溶液)中而求出。 According to JIS (Japanese Industrial Standards; Japanese Industrial Standards) K7112, the membrane was immersed in a density gradient solution (aqueous calcium nitrate solution) to obtain it.

[熱水熱收縮率] [Hot water thermal shrinkage rate]

將膜以沿著長度方向及其正交方向(寬度方向)的方式裁斷為10cm×10cm之正方形，於90℃±0.5℃之熱水中，以無負載狀態浸漬10秒而使其熱收縮後，立即於25℃±0.5℃之水中浸漬10秒，然後自水中抽出，測定試樣之縱向及橫向之長度，為根據下述式所求出之值。 The film was cut into a square of 10cm×10cm along the longitudinal direction and its orthogonal direction (width direction), and was immersed in hot water at 90°C±0.5°C for 10 seconds in an unloaded state to heat shrink it. , Immediately immerse it in water at 25°C ± 0.5°C for 10 seconds, then extract it from the water, measure the longitudinal and transverse lengths of the sample, and obtain the values according to the following formula.

收縮率={(收縮前之長度-收縮後之長度)/收縮前之長度}×100(%) Shrinkage rate={(Length before shrinkage-Length after shrinkage)/Length before shrinkage}×100(%)

本實施例中，膜之收縮率最大之方向(主收縮方向)為寬度方向。 In this embodiment, the direction in which the shrinkage rate of the film is the largest (main shrinkage direction) is the width direction.

〔玻璃轉移點(Tg)〕 [Glass transition point (Tg)]

使用精工電子工業股份有限公司製造之示差掃描熱量計(型號：DSC220)，根據JIS K7121而求出。將未延伸膜10mg以升溫速度10℃/分鐘自25℃升溫至120℃，獲得升溫分佈。將玻璃轉移溫度以下之基準線之延長線與表示躍遷部中之最大傾斜之切線的交點之溫度設為玻璃轉移溫度。 It calculated|required based on JIS K7121 using the differential scanning calorimeter (model: DSC220) by Seiko Instruments Inc.. 10 mg of the unstretched film was heated from 25°C to 120°C at a temperature increase rate of 10°C/min to obtain a temperature increase profile. The temperature of the intersection of the extension line of the reference line below the glass transition temperature and the tangent line showing the maximum inclination in the transition portion was defined as the glass transition temperature.

〔溶劑黏接方法〕 [Solvent bonding method]

將膜裁斷為寬度380mm且長度方向之卷長為1000m而製造出膜卷。將膜自該膜卷捲出，將黏接用溶劑組成物以塗佈寬度為4±2mm之範圍內的方式沿長度方向連續地塗佈於膜寬度方向之一端部之內側，並以重疊部位於中心的方式將膜折疊而將該溶劑組成物塗佈部溶劑黏接於膜之另一寬度方向端部之上。 The film was cut into a width of 380 mm and the roll length in the longitudinal direction was 1000 m to produce a film roll. The film is unrolled from the film roll, and the adhesive solvent composition is continuously applied to the inner side of one end in the width direction of the film in a manner that the coating width is within the range of 4±2 mm along the length direction. The film is folded so as to be located in the center, and the solvent composition coating portion is solvent-bonded on the other end of the film in the width direction.

溶劑黏接加工速度設為400m/分鐘，將溶劑黏接後之膜以相同速度捲繞為紙管。將所獲得之管狀標籤之捲於23℃之氛圍下熟化24小時。而且，溶劑之塗佈量任意地進行調整。 The solvent bonding processing speed was set to 400 m/min, and the film after solvent bonding was wound into a paper tube at the same speed. The obtained roll of the tubular label was aged for 24 hours in an atmosphere of 23°C. Furthermore, the coating amount of the solvent is arbitrarily adjusted.

〔溶劑組成物之黏度〕 [Viscosity of solvent composition]

使用愛宕(Atago)股份有限公司製造之B型黏度計(型號：BASE L)，於溶劑組成物溫度23℃、轉數10rpm之條件下進行測定。 The measurement was performed under the conditions of a solvent composition temperature of 23° C. and a rotation number of 10 rpm using a B-type viscometer (model: BASE L) manufactured by Atago Co., Ltd.

〔溶劑之穿透性評價〕 [Evaluation of Penetration of Solvents]

利用手將經溶劑黏接而獲得之熟化後的卷長1000m之管狀標籤自卷表面抽出500m，當出現黏連現象時判斷為溶劑穿透，且如以下般進行評價。 The aged tubular label with a roll length of 1000 m obtained by solvent bonding was pulled out 500 m from the surface of the roll by hand, and when the sticking phenomenon occurred, it was judged that the solvent penetrated, and the evaluation was carried out as follows.

無黏連：溶劑之穿透性評價○(無穿透) No sticking: Evaluation of solvent penetration ○ (no penetration)

有黏連：溶劑之穿透性評價×(有穿透) With adhesion: Evaluation of penetration of solvent × (with penetration)

〔溶劑黏接部之剝離強度之測定方法〕 [Method for Determination of Peel Strength of Solvent Bonded Parts]

從上述溶劑穿透評價時自卷表層抽出500m後之卷長500m之管狀標籤卷之表層部分，以溶劑黏接部位於中央的方式將寬度(相當於長度方向長度)15mm之試樣沿著圓周方向切下(長度為100mm左右即可)。試樣數n設為10。放置於鮑爾溫(Baldwin)公司製造之萬能拉伸試驗機「STM-50」，於拉伸速度200mm/分鐘之條件下進行180°剝離試驗。將10個試樣之平均值設為溶劑黏接部之剝離強度(N/15mm)。 From the surface layer part of the tubular label roll with a roll length of 500m after pulling out 500m from the surface layer of the roll during the above-mentioned solvent penetration evaluation, a sample with a width (corresponding to the length in the longitudinal direction) of 15mm is placed along the circumference so that the solvent bonding part is located in the center Cut in the direction (the length is about 100mm). The number of samples n was set to 10. It was placed in a universal tensile testing machine "STM-50" manufactured by Baldwin Corporation, and a 180° peel test was performed at a tensile speed of 200 mm/min. The average value of 10 samples was taken as the peel strength (N/15mm) of the solvent-bonded part.

<聚酯A至聚酯G、聚酯I至聚酯J之合成例> <Synthesis example of polyester A to polyester G, polyester I to polyester J>

向具備攪拌機、溫度計及部分環流式冷卻器之不銹鋼製高壓釜中，以乙二醇按莫耳比計為對苯二甲酸二甲酯之2.2倍的方式添加作為二接酸成分之對苯二甲酸二甲酯(DMT)100莫耳%、作為多元醇成分之乙二醇(EG)100莫 耳%，使用0.05莫耳%(相對於酸成分)乙酸鋅作為酯交換觸媒，一邊將所生成之甲醇向系外蒸餾去除一邊進行酯交換反應。然後，添加作為縮聚觸媒之三氧化二銻0.225莫耳%(相對於酸成分)，於280℃且26.7Pa之減壓條件下進行縮聚反應，獲得固有黏度0.70dl/g之聚酯A。該聚酯A係聚對苯二甲酸乙二酯。另外，於上述聚酯A之製造時，將作為潤滑劑之SiO2(富士矽公司製造之Sylysia(266)相對於聚酯添加8000ppm。而且，與上述同樣地，合成表1所示之聚酯B、C、D、I、J與表2所示之聚酯E、F、G。而且，作為PET瓶再利用原料，使用「Clear Pellet」(與野PET瓶再利用公司製造；固有黏度0.63dl/g)作為碎片H。 To a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial circulation cooler, terephthalic acid was added as a diacid component so that ethylene glycol was 2.2 times the molar ratio of dimethyl terephthalate. Dimethyl formate (DMT) 100 mol %, ethylene glycol (EG) as a polyol component 100 mol %, and 0.05 mol % (with respect to acid component) zinc acetate as a transesterification catalyst, all The transesterification reaction was performed while the produced methanol was distilled out of the system. Then, 0.225 mol% of antimony trioxide (relative to the acid component) was added as a polycondensation catalyst, and a polycondensation reaction was carried out at 280° C. and a reduced pressure of 26.7 Pa to obtain polyester A with an intrinsic viscosity of 0.70 dl/g. The polyester A is polyethylene terephthalate. In addition, 8000 ppm of SiO 2 (Sylysia (266) manufactured by Fuji Silicon Co., Ltd.) was added to the polyester as a lubricant during the production of the above-mentioned polyester A. Furthermore, the polyesters shown in Table 1 were synthesized in the same manner as above. B, C, D, I, J, and polyesters E, F, and G shown in Table 2. Also, as a raw material for PET bottle recycling, "Clear Pellet" (manufactured by Yono PET Bottle Recycling Co., Ltd.; intrinsic viscosity 0.63) was used. dl/g) as fragment H.

表中，TPA為對苯二甲酸，IPA為間苯二甲酸，OPA為鄰苯二甲酸，AA為丙烯酸，SA為癸二酸，CHDM為1,4-環己烷二甲醇，NPG為新戊二醇，BD為1,4-丁二醇。表1及表2之聚酯之固有黏度係聚酯A為0.70dl/g，聚酯B為0.70dl/g，聚酯C為0.73dl/g，聚酯D為0.73dl/g，聚酯E為0.53dl/g，聚酯F為0.98dl/g，聚酯G為0.89dl/g，聚酯H為0.63dl/g，聚酯I為0.70dl/g，聚酯H為0.70dl/g。另外，各聚酯適宜設為碎片狀。 In the table, TPA is terephthalic acid, IPA is isophthalic acid, OPA is phthalic acid, AA is acrylic acid, SA is sebacic acid, CHDM is 1,4-cyclohexanedimethanol, and NPG is neopentyl Diol, BD is 1,4-butanediol. The intrinsic viscosity of the polyesters in Tables 1 and 2 is 0.70 dl/g for polyester A, 0.70 dl/g for polyester B, 0.73 dl/g for polyester C, 0.73 dl/g for polyester D, and 0.73 dl/g for polyester D. E was 0.53 dl/g, polyester F was 0.98 dl/g, polyester G was 0.89 dl/g, polyester H was 0.63 dl/g, polyester I was 0.70 dl/g, and polyester H was 0.70 dl/g g. In addition, each polyester is preferably in the form of chips.

Figure 106143366-A0202-12-0024-1
Figure 106143366-A0202-12-0024-1
Figure 106143366-A0202-12-0025-2
Figure 106143366-A0202-12-0025-2

Figure 106143366-A0202-12-0025-3
Figure 106143366-A0202-12-0025-3

<膜I之製造方法> <Manufacturing method of film I>

對上述合成例中獲得之各聚酯碎片個別地進行預備乾燥，如表3所示，將聚酯A以5質量%、聚酯B以5質量%及聚酯C以90質量%進行混合後投入至擠出機中。使該混合樹脂以280℃熔融後自T型模擠出，與表面溫度已冷卻至30℃之進行旋轉的金屬輥接觸而進行急冷，藉此獲得厚度60μm之未延伸膜。將膜中之非晶成分量表示於表3。此時之未延伸膜之拉取速度(金屬輥之旋轉速度)約為20m/min。 The polyester chips obtained in the above synthesis examples were individually pre-dried, and as shown in Table 3, 5 mass % of polyester A, 5 mass % of polyester B, and 90 mass % of polyester C were mixed. put into the extruder. The mixed resin was melted at 280°C, extruded from a T-die, contacted with a rotating metal roll whose surface temperature was cooled to 30°C, and quenched to obtain an unstretched film with a thickness of 60 μm. Table 3 shows the amount of amorphous components in the film. The drawing speed (rotation speed of the metal roll) of the unstretched film at this time was about 20 m/min.

將上述未延伸膜向拉幅機導引，於預熱區域加熱至100℃，於78℃之設定溫度之延伸區域沿寬度方向延伸5倍。繼而以82℃進行5秒熱處理，然後進行冷卻。將兩緣部裁斷去除而以寬度500mm捲繞成卷狀，藉此跨及1100m之長度連續地製造厚度12μm之橫向單軸延伸膜。 所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 The above-mentioned unstretched film was guided to a tenter, heated to 100° C. in a preheating zone, and stretched 5 times in the width direction in a stretched zone at a predetermined temperature of 78° C. Next, it heat-processes at 82 degreeC for 5 seconds, and it cools. Both edge parts were cut and removed, and the width 500mm was wound into a roll shape, and the transverse uniaxially stretched film of thickness 12micrometer was continuously manufactured over the length of 1100m. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜II之製造方法> <Manufacturing method of film II>

使用聚酯D以代替聚酯C，且將未延伸膜之厚度自60μm變更為200μm，除此以外，利用與膜I相同之方法跨及1100m之長度連續地製造厚度40μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 A laterally uniaxially stretched film with a thickness of 40 μm was continuously produced by the same method as in Film I, except that polyester D was used instead of polyester C, and the thickness of the unstretched film was changed from 60 μm to 200 μm. . The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜III之製造方法> <Manufacturing method of film III>

使用5質量%之聚酯A、25質量%之聚酯C及70質量%之聚酯H，將未延伸膜之厚度自60μm變更為64μm，延伸倍率自5倍變更為4倍，除此以外，利用與膜I相同之方法跨及1100m之長度連續地製造厚度16μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 Using 5 mass % of polyester A, 25 mass % of polyester C, and 70 mass % of polyester H, the thickness of the unstretched film was changed from 60 μm to 64 μm, and the stretching ratio was changed from 5 times to 4 times, except that , a transverse uniaxially stretched film with a thickness of 16 μm was continuously produced across a length of 1100 m using the same method as Film I. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜IV之製造方法> <Manufacturing method of film IV>

對上述合成例中獲得之各聚酯碎片個別地進行預備乾燥，如表3所示，將聚酯A以5質量%、聚酯I以95質量%進行混合後投入至擠出機。使該混合樹脂以280℃熔融後自T型模擠出，與表面溫度已冷卻至30℃之進行旋轉之金屬輥接觸而進行急冷，藉此獲得厚度100μm之未延伸膜。將膜中之非晶成分量表示於表3。此時之未延 伸膜之拉取速度(金屬輥之旋轉速度)約為20m/min。 The polyester chips obtained in the above synthesis examples were individually pre-dried, and as shown in Table 3, polyester A was mixed at 5 mass % and polyester I was mixed at 95 mass % and charged into an extruder. The mixed resin was melted at 280°C, extruded from a T-die, and quenched in contact with a rotating metal roll whose surface temperature was cooled to 30°C, thereby obtaining an unstretched film with a thickness of 100 μm. Table 3 shows the amount of amorphous components in the film. The drawing speed (rotation speed of the metal roll) of the unstretched film at this time was about 20 m/min.

將上述未延伸膜向拉幅機導引，於預熱區域加熱至90℃，於70℃之設定溫度之延伸區域沿寬度方向延伸5倍。繼而於78℃下進行5秒熱處理，然後進行冷卻。將兩緣部裁斷除去而以寬度500mm捲繞成卷狀，藉此跨及1100m連續地製造厚度20μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 The above-mentioned unstretched film was guided to a tenter, heated to 90° C. in a preheating zone, and stretched 5 times in the width direction in a stretching zone at a set temperature of 70° C. Next, it heat-processes at 78 degreeC for 5 seconds, and it cools. Both edge parts were cut and removed, and the width|variety 500mm was wound into a roll shape, and the transverse uniaxially stretched film of thickness 20micrometer was continuously manufactured over 1100m. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜V之製造方法> <Manufacturing method of film V>

聚酯I改為聚酯J，而獲得厚度100μm之未延伸膜。將未延伸膜向拉幅機導引，於預熱區域加熱至97℃，於77℃之設定溫度之延伸區域沿寬度方向延伸5倍。繼而於85℃下進行5秒熱處理，然後進行冷卻。將兩緣部裁斷除去而以寬度500mm捲繞成卷狀，藉此跨及1100m連續地製造厚度20μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 Polyester I was changed to polyester J to obtain an unstretched film with a thickness of 100 μm. The unstretched film was guided to a tenter, heated to 97° C. in a preheating zone, and stretched 5 times in the width direction in the stretch zone at a set temperature of 77° C. Next, it heat-processes at 85 degreeC for 5 seconds, and it cools. Both edge parts were cut and removed, and the width|variety 500mm was wound into a roll shape, and the transverse uniaxially stretched film of thickness 20micrometer was continuously manufactured over 1100m. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜VI之製造方法> <Manufacturing method of film VI>

使用5質量%之聚酯A、70質量%之聚酯I及25質量%之聚酯H，獲得厚度100μm之未延伸膜。將未延伸膜向拉幅機導引，於預熱區域加熱至93℃，於73℃之設定溫度之延伸區域沿寬度方向延伸5倍。繼而於81℃下進行5秒熱處理，然後進行冷卻。將兩緣部裁斷除去而以寬度500mm捲繞成卷狀，藉此跨及1100m連續地製造厚度 20μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 Using 5 mass % of polyester A, 70 mass % of polyester I, and 25 mass % of polyester H, an unstretched film having a thickness of 100 μm was obtained. The unstretched film was guided to the tenter, heated to 93° C. in the preheating zone, and stretched 5 times in the width direction in the stretch zone at the set temperature of 73° C. Next, it heat-processed at 81 degreeC for 5 seconds, and it cooled. Both edges were cut and removed, and the film was wound into a roll with a width of 500 mm, thereby continuously producing a transversely uniaxially stretched film with a thickness of 20 µm over a span of 1100 m. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

<膜VII之製造方法> <Manufacturing method of film VII>

利用共擠出法將芯層形成用樹脂、表層形成用樹脂、黏接劑層形成用樹脂自各個擠出機(第一擠出機至第三擠出機)熔融擠出，於模具(T型模)內積層，並利用氣刀法繞在已冷卻至30℃之進行旋轉之金屬輥而進行急冷，藉此獲得厚度100μm之三種五層構成，亦即，於芯層之表背兩側積層有中間層(黏接劑層)且於該等中間層之外側分別積層有表層之構成的未延伸膜(聚苯乙烯系樹脂積層片)。未延伸膜之各層之形成方法(至熔融擠出為止之步驟)為以下所示。另外，以下之說明中，自聚苯乙烯系混合樹脂積層片之表背起依序稱作第一層、第二層、第三層、第四層、第五層(亦即第五層之表面為金屬輥接觸面)。此時之未延伸膜之拉取速度(金屬輥之旋轉速度)約為20m/min。 The resin for forming the core layer, the resin for forming the skin layer, and the resin for forming the adhesive layer are melt-extruded from each extruder (the first extruder to the third extruder) by the co-extrusion method, and are placed in a die (T The mold) was internally laminated, and quenched by the air knife method around a rotating metal roll that had been cooled to 30 ° C, thereby obtaining three types of five-layer structures with a thickness of 100 μm, that is, on both sides of the front and back of the core layer. An unstretched film (polystyrene resin laminate sheet) having an intermediate layer (adhesive layer) is laminated and a surface layer is laminated on the outer sides of the intermediate layers, respectively. The formation method of each layer of the unstretched film (steps up to melt extrusion) is shown below. In addition, in the following description, it is called the first layer, the second layer, the third layer, the fourth layer, the fifth layer (that is, the fifth layer) in order from the front and back of the polystyrene-based mixed resin laminated sheet. The surface is the metal roller contact surface). The drawing speed (rotation speed of the metal roll) of the unstretched film at this time was about 20 m/min.

‧第一層、第五層(表層)之形成 ‧The formation of the first layer and the fifth layer (surface layer)

於分別使用摻合機裝置對上述聚酯A與聚酯I進行預備乾燥後，將該預備乾燥後之聚酯A以5質量份且聚酯I以95質量份於摻合機中混合，然後利用定量螺旋進料器連續地供給至第一擠出機之正上方之料斗。然後，將所供給之聚酯A及聚酯I之混合物自單軸式第一擠出機之T型模以280℃熔融擠出(以積層於中間層之外側的方式熔融擠出，該中間層積層於芯層之表背之外側)。為了使自T型模之擠出穩定，而向擠出機與T型模之間***螺旋型且並列 型之齒輪泵。 After pre-drying the above polyester A and polyester I using a blender device, 5 parts by mass of polyester A and 95 parts by mass of polyester I were mixed in a blender, and then It was continuously supplied to the hopper directly above the first extruder by means of a quantitative screw feeder. Then, the supplied mixture of polyester A and polyester I was melt-extruded from the T-die of the uniaxial first extruder at 280° C. Laminate layers on the outside of the front and back of the core layer). In order to stabilize the extrusion from the T-die, a helical and side-by-side gear pump was inserted between the extruder and the T-die.

‧第二層、第四層(黏接劑層)之形成 ‧The formation of the second and fourth layers (adhesive layer)

於使用摻合機裝置對碎片K進行預備乾燥後，利用定量螺旋進料器將該預備乾燥後之碎片K連續地供給至第二擠出機之正上方之料斗。然後，將所供給之碎片H自單軸式第二擠出機之T型模熔融擠出(以積層於芯層之表背之外側的方式熔融擠出)。另外，第二擠出機之溫度調整為200℃。而且，與利用第一擠出機進行之擠出同樣地，為了使自T型模之擠出穩定，而向擠出機與T型模之間***螺旋型且並列型之齒輪泵。 After preliminarily drying the chips K using a blender device, the preliminarily dried chips K were continuously supplied to a hopper directly above the second extruder using a quantitative screw feeder. Then, the supplied chips H were melt-extruded from the T-die of the uniaxial second extruder (melt-extruded so as to be laminated on the outside of the front and back of the core layer). In addition, the temperature of the second extruder was adjusted to 200°C. Furthermore, like the extrusion by the first extruder, in order to stabilize the extrusion from the T-die, a screw-type and parallel-type gear pump was inserted between the extruder and the T-die.

‧第三層(芯層)之形成 ‧The formation of the third layer (core layer)

於使用摻合機裝置分別對碎片L、M、N進行預備乾燥後，利用定量螺旋進料器將該等碎片L、M、N連續且分別地供給至混合摻合機內。另外，將碎片L之供給量設為43質量%份，碎片M之供給量設為43質量%份，碎片N之供給量設為14質量%份。然後，利用定量螺旋進料器將已於混合摻合機內混合之碎片L、M、N之混合原料連續且分別地供給至第三擠出機之正上方之料斗。然後，將所供給之碎片L、M、N(經混合者)自單軸式第三擠出機之T型模熔融擠出。另外，第三擠出機之溫度亦調整為200℃。而且，與利用第一擠出機進行之擠出或利用第二擠出機進行之擠出同樣地，為了使自T型模之擠出穩定，而向擠出機與T型模之間***螺旋型且並列型之齒輪泵。 After preliminarily drying the pieces L, M, and N using a blender device, the pieces L, M, and N are continuously and individually supplied into the mixing blender using a quantitative screw feeder. In addition, the supply amount of the chips L was 43 parts by mass, the supply amount of the chips M was 43 parts by mass, and the supply amount of the chips N was 14 parts by mass. Then, the mixed raw materials of the chips L, M, and N that have been mixed in the mixing blender were continuously and separately supplied to the hopper directly above the third extruder using a quantitative screw feeder. Then, the supplied pieces L, M, N (mixed) were melt extruded from the T-die of the single-shaft third extruder. In addition, the temperature of the third extruder was also adjusted to 200°C. Furthermore, in the same way as the extrusion with the first extruder or the extrusion with the second extruder, in order to stabilize the extrusion from the T-die, an insert is inserted between the extruder and the T-die. Spiral and parallel gear pumps.

另外，利用上述各擠出機進行之樹脂之擠出中，未延伸膜之形成中的第一擠出機至第三擠出機之吐出量係以第一層/第二層/第三層/第四層/第五層之厚度比率為 24/2/48/2/24的方式進行調整。 In addition, in the resin extrusion by each of the above-mentioned extruders, the discharge amount from the first extruder to the third extruder in the formation of the unstretched film is the first layer/second layer/third layer. The thickness ratio of the / fourth layer / fifth layer is adjusted to 24/2/48/2/24.

將所獲得之未延伸膜於預熱區域加熱至100℃，於80℃之設定溫度之延伸區域沿寬度方向延伸5倍。繼而，以88℃進行5秒熱處理，然後進行冷卻。將兩緣部裁斷去除而以寬度500mm捲繞成卷狀，藉此跨及1100m連續地製造厚度20μm之橫向單軸延伸膜。所獲得之膜係僅於寬度方向上熱收縮之熱收縮性聚酯系膜。將90℃下測定出之熱水熱收縮率表示於表3。 The obtained unstretched film was heated to 100°C in a preheating zone, and the stretched zone at a set temperature of 80°C was stretched 5 times in the width direction. Next, it heat-processed for 5 second at 88 degreeC, and it cooled. Both edge parts were cut and removed, and the width|variety 500mm was wound into a roll shape, and the transverse uniaxially stretched film of thickness 20micrometer was continuously manufactured over 1100m. The obtained film is a heat-shrinkable polyester film that heat-shrinks only in the width direction. Table 3 shows the hot water thermal shrinkage rate measured at 90°C.

Figure 106143366-A0202-12-0030-4
Figure 106143366-A0202-12-0030-4

[實施例1] [Example 1]

將1,3-二氧雜環戊烷/丙酮/聚酯E以22/68/10(質量比)混合而成的溶劑組成物以4mm寬度且成為300mg/m2的方式塗佈於膜I，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表4。成為無溶劑之穿透且溶劑黏接部之剝離強度大 之良好之標籤。 The solvent composition in which 1,3-dioxolane/acetone/polyester E was mixed in 22/68/10 (mass ratio) was applied to the film I with a width of 4 mm and 300 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min to obtain a tubular label roll. Furthermore, the presence or absence of solvent penetration and the peeling strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 4. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例2] [Example 2]

除將1,3-二氧雜環戊烷/丙酮/聚酯E以45/45/10(質量比)混合而成的溶劑組成物以100mg/m2的方式塗佈以外，與實施例1同樣地進行評價。將溶劑黏接條件及結果表示於表4。均成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The same procedure as Example 1 except that the solvent composition obtained by mixing 1,3-dioxolane/acetone/polyester E at 45/45/10 (mass ratio) was applied at 100 mg/m 2 Evaluation is performed in the same manner. The solvent bonding conditions and results are shown in Table 4. All of them become good labels with no penetration of solvent and high peel strength of solvent-bonded part.

[實施例3至實施例8] [Example 3 to Example 8]

將膜及溶劑組成物之調配比率進行各種變更，與實施例1同樣地進行評價。將各實施例之溶劑黏接條件及結果表示於表4。均成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 Various changes were made to the mixing ratio of the film and the solvent composition, and the evaluation was carried out in the same manner as in Example 1. The solvent bonding conditions and results of each example are shown in Table 4. All of them become good labels with no penetration of solvent and high peel strength of solvent-bonded part.

[比較例1] [Comparative Example 1]

除使用僅為1,3-二氧雜環戊烷之溶劑以外，與實施例1同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表4。有溶劑之穿透，從而作為標籤欠佳。 A tubular label roll was obtained in the same manner as in Example 1, except that a solvent containing only 1,3-dioxolane was used. The solvent bonding conditions and results are shown in Table 4. There is penetration of the solvent, which is not good as a label.

[比較例2] [Comparative Example 2]

除使用將1,3-二氧雜環戊烷/丙酮以50/50(質量比)混合而成的溶劑組成物以外，與實施例1同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表4。雖無溶劑之穿透，但溶劑黏接部之剝離強度較小，作為標籤欠佳。 A tubular label roll was obtained in the same manner as in Example 1, except that a solvent composition in which 1,3-dioxolane/acetone was mixed at 50/50 (mass ratio) was used. The solvent bonding conditions and results are shown in Table 4. Although there is no penetration of the solvent, the peel strength of the solvent-bonded part is small, which is not good as a label.

[比較例3] [Comparative Example 3]

除膜III中使用僅為1,3-二氧雜環戊烷之溶劑以外，與實施例1同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表4。雖無溶劑之穿透，但溶劑黏接部之剝離強度較小，作為標籤欠佳。 A tubular label roll was obtained in the same manner as in Example 1, except that a solvent containing only 1,3-dioxolane was used for the film III. The solvent bonding conditions and results are shown in Table 4. Although there is no penetration of the solvent, the peel strength of the solvent-bonded part is small, which is not good as a label.

[比較例4] [Comparative Example 4]

除使用將1,3-二氧雜環戊烷/聚酯F以70/30(重量比)混合而成的溶劑組成物以外，與實施例1同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表4。因溶劑組成物之黏度過高，故無法將溶劑組成物以4mm寬度且成為50mg/m2以上的方式塗佈於膜。 A tubular label roll was obtained in the same manner as in Example 1, except that a solvent composition obtained by mixing 1,3-dioxolane/polyester F at 70/30 (weight ratio) was used. The solvent bonding conditions and results are shown in Table 4. Since the viscosity of the solvent composition was too high, it was not possible to apply the solvent composition to a film with a width of 4 mm and 50 mg/m 2 or more.

Figure 106143366-A0202-12-0032-5
Figure 106143366-A0202-12-0032-5

[實施例9] [Example 9]

將THF/聚酯E以90/10(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜IV，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester E at 90/10 (mass ratio) was applied to the film IV with a width of 4 mm and 250 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例10] [Example 10]

將THF/聚酯F以80/20(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜IV，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester F at 80/20 (mass ratio) was applied to the film IV with a width of 4 mm and 250 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min. Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent-bonded conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例11] [Example 11]

將THF/聚酯G以95/5(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜IV，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester G at 95/5 (mass ratio) was applied to the film IV with a width of 4 mm and 250 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例12] [Example 12]

將THF/聚酯E以60/40(質量比)混合而成的溶劑組成物以4mm寬度且成為100mg/m2的方式塗佈於膜IV，以 加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester E at 60/40 (mass ratio) was applied to the film IV with a width of 4 mm and 100 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例13] [Example 13]

將THF/聚酯E以90/10(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜V，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester E at 90/10 (mass ratio) was applied to the film V with a width of 4 mm and 250 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例14] [Example 14]

將THF/聚酯F以80/20(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜VI，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester F at 80/20 (mass ratio) was applied to the film VI with a width of 4 mm and 250 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例15] [Example 15]

將THF/聚酯E以60/40(質量比)混合而成的溶劑組成物以4mm寬度且成為100mg/m2的方式塗佈於膜VI，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶 劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition obtained by mixing THF/polyester E at 60/40 (mass ratio) was applied to the film VI with a width of 4 mm and 100 mg/m 2 , and solvent bonding was performed at a processing speed of 400 m/min, and Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent bonding conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[實施例16] [Example 16]

將THF/聚酯E以90/10(質量比)混合而成的溶劑組成物以4mm寬度且成為250mg/m2的方式塗佈於膜VII，以加工速度400m/分鐘進行溶劑黏接，而獲得管狀標籤卷。而且，利用上述方法測定有無溶劑穿透、溶劑黏接部之剝離強度，並將溶劑黏接條件及結果表示於表5。成為無溶劑之穿透且溶劑黏接部之剝離強度大之良好之標籤。 The solvent composition formed by mixing THF/polyester E with 90/10 (mass ratio) is applied to the film VII with a width of 4 mm and a mode of 250 mg/m 2 , and solvent bonding is performed at a processing speed of 400 m/min. Obtain tubular label rolls. Furthermore, the presence or absence of solvent penetration and the peel strength of the solvent-bonded portion were measured by the above-mentioned method, and the solvent-bonded conditions and results are shown in Table 5. It becomes a good label with no penetration of the solvent and high peel strength of the solvent-bonded part.

[比較例5] [Comparative Example 5]

除使用僅為THF之溶劑以外與實施例12同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表5。溶劑黏接部之剝離強度較低，作為標籤欠佳。 A tubular label roll was obtained in the same manner as in Example 12, except that the solvent only THF was used. The solvent bonding conditions and results are shown in Table 5. The peel strength of the solvent-bonded part is low, which is not good as a label.

[比較例6] [Comparative Example 6]

除使用僅為THF之溶劑以外與實施例15同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表5。溶劑黏接部之剝離強度較低，作為標籤欠佳。 A tubular label roll was obtained in the same manner as in Example 15, except that the solvent only THF was used. The solvent bonding conditions and results are shown in Table 5. The peel strength of the solvent-bonded part is low, which is not good as a label.

[比較例7] [Comparative Example 7]

除使用將THF/聚酯G以40/60(質量比)混合而成的溶劑組成物以外，與實施例9同樣地獲得管狀標籤卷。將溶劑黏接條件及結果表示於表5。因溶劑組成物之黏度過高，故無法將溶劑組成物以4mm寬度且成為1g/m2以下的方式塗佈於膜。 A tubular label roll was obtained in the same manner as in Example 9, except that the solvent composition obtained by mixing THF/polyester G at 40/60 (mass ratio) was used. The solvent bonding conditions and results are shown in Table 5. Since the viscosity of the solvent composition was too high, the solvent composition could not be applied to the film with a width of 4 mm and 1 g/m 2 or less.

Figure 106143366-A0202-12-0036-6
Figure 106143366-A0202-12-0036-6

(產業可利用性) (Industrial Availability)

本發明之熱收縮性聚酯系標籤能夠應對以削減垃圾量為目的的薄壁化之需求，且，不易引起溶劑穿透等不良情況，而且，黏接部之剝離強度高，因而可有效用作飲料瓶之標籤。而且，即便使用較多地使用了結晶性高之PET瓶再利用原料之熱收縮性聚酯系膜，溶劑黏接部之剝離強度亦高，因而就該點而言，亦可有效用作飲料瓶之標籤。 The heat-shrinkable polyester label of the present invention can meet the requirement of thinning for the purpose of reducing the amount of waste, and is less likely to cause problems such as solvent penetration, and has high peel strength of the adhesive portion, so it can be effectively used Labels for beverage bottles. In addition, even if a heat-shrinkable polyester-based film is used, which uses the recycled raw material of PET bottles with high crystallinity, the peeling strength of the solvent-bonded part is also high, so it can be effectively used as a beverage in this regard. bottle label.

Claims (8)

一種熱收縮性聚酯系標籤，其係熱收縮性聚酯系膜之兩端部彼此利用溶劑組成物黏接而成之管狀之熱收縮性聚酯系標籤，前述溶劑組成物係至少包含1,3-二氧雜環戊烷及/或四氫呋喃與聚酯之溶劑組成物，前述黏接部之剝離強度為2N/15mm以上。 A heat-shrinkable polyester-based label, which is a tubular heat-shrinkable polyester-based label in which both ends of a heat-shrinkable polyester-based film are bonded by a solvent composition, wherein the solvent composition at least comprises 1 , The solvent composition of 3-dioxolane and/or tetrahydrofuran and polyester, the peel strength of the aforementioned bonding part is 2N/15mm or more. 如請求項1所記載之熱收縮性聚酯系標籤，其中前述溶劑組成物中所含之聚酯之含量為1質量%以上40質量%以下。 The heat-shrinkable polyester label according to claim 1, wherein the content of the polyester contained in the solvent composition is 1 mass % or more and 40 mass % or less. 如請求項1或2中任一項所記載之熱收縮性聚酯系標籤，其中前述熱收縮性聚酯系膜之厚度為5μm以上60μm以下。 The heat-shrinkable polyester-based label according to any one of claims 1 or 2, wherein the thickness of the heat-shrinkable polyester-based film is 5 μm or more and 60 μm or less. 如請求項1或2所記載之熱收縮性聚酯系標籤，其中包含至少表層具有前述熱收縮性聚酯系膜之積層膜。 The heat-shrinkable polyester-based label according to claim 1 or 2, comprising a laminate film having at least a surface layer of the heat-shrinkable polyester-based film. 如請求項3所記載之熱收縮性聚酯系標籤，其中包含至少表層具有前述熱收縮性聚酯系膜之積層膜。 The heat-shrinkable polyester-based label according to claim 3, comprising a laminate film having the heat-shrinkable polyester-based film at least on the surface layer. 一種包裝體，係於包裝對象物之外周之至少一部分具有如請求項1至5中任一項所記載之熱收縮性聚酯系標籤。 A packaging body having the heat-shrinkable polyester label according to any one of Claims 1 to 5 on at least a part of the outer periphery of an object to be packaged. 一種熱收縮性聚酯系標籤的製造方法，係利用至少包含1,3-二氧雜環戊烷及/或四氫呋喃與聚酯之溶劑組成物，將熱收縮性聚酯系膜之兩端部重合並黏接。 A method for producing a heat-shrinkable polyester-based label, comprising at least a solvent composition comprising 1,3-dioxolane and/or tetrahydrofuran and polyester, to separate both ends of a heat-shrinkable polyester-based film Overlap and glue. 一種熱收縮性聚酯系標籤用溶劑組成物，係至少包含1,3-二氧雜環戊烷及/或四氫呋喃與聚酯之黏度小於100mPa‧s之溶劑組成物，用於藉由上述溶劑組成物將熱收縮性膜黏接而作成熱收縮性聚酯系標籤。 A solvent composition for a heat-shrinkable polyester label, which at least contains 1,3-dioxolane and/or tetrahydrofuran and a solvent composition with a viscosity of less than 100 mPa·s of polyester, which is used for the above-mentioned solvent The composition adheres a heat-shrinkable film to form a heat-shrinkable polyester label.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101263171A (en) * 2005-09-14 2008-09-10 旭化成化学株式会社 Block copolymer and process for production of thermally shrinkable film
TW201621013A (en) * 2014-09-09 2016-06-16 東洋紡股份有限公司 Heat-shrinkable polyester-based label, package, and process for producing heat-shrinkable polyester-based label
CN106163768A (en) * 2014-04-01 2016-11-23 东洋纺株式会社 Heat-contractable ployester series film and package body

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5610451A (en) * 1979-07-05 1981-02-02 Toray Industries Resin coated metallic plate for vessel
EP0210646B2 (en) * 1985-07-31 1998-01-28 Toyo Boseki Kabushiki Kaisha Thermo-shrinkable polyester type film and tube and processing method for preparing the tube
JP3075019B2 (en) 1993-06-10 2000-08-07 東洋紡績株式会社 Method for producing heat-shrinkable polyester tube
JP3452021B2 (en) 1993-06-10 2003-09-29 東洋紡績株式会社 Heat-shrinkable polyester tube and heat-shrinkable polyester tube
JPH0782389A (en) * 1993-09-14 1995-03-28 Mitsubishi Rayon Co Ltd Thermally shrinkable polyester film
JPH09176612A (en) * 1995-12-27 1997-07-08 Toagosei Co Ltd Solvent-base adhesive
JP3075019U (en) 2000-07-21 2001-02-09 君夫 佐藤 Powder clutch
KR101255388B1 (en) * 2005-04-08 2013-04-17 도요보 가부시키가이샤 Heat-shrinkable polyester film and heat-shrinkable labels
JP5151015B2 (en) * 2005-08-25 2013-02-27 東洋紡株式会社 Heat-shrinkable polyester film and label and method for producing the same
WO2009084212A1 (en) * 2007-12-27 2009-07-09 Fuji Seal International, Inc. Shrink film and cylindrical shrink label
US8778077B2 (en) * 2012-02-29 2014-07-15 Skc Inc. Solvent for heat-shrinkable polyester-based labels
JP5947153B2 (en) 2012-08-28 2016-07-06 ヘンケルジャパン株式会社 Hot melt adhesive
JP6050170B2 (en) * 2013-03-27 2016-12-21 富士フイルム株式会社 Laminate for temporary bonding for manufacturing semiconductor device and method for manufacturing semiconductor device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101263171A (en) * 2005-09-14 2008-09-10 旭化成化学株式会社 Block copolymer and process for production of thermally shrinkable film
CN106163768A (en) * 2014-04-01 2016-11-23 东洋纺株式会社 Heat-contractable ployester series film and package body
TW201621013A (en) * 2014-09-09 2016-06-16 東洋紡股份有限公司 Heat-shrinkable polyester-based label, package, and process for producing heat-shrinkable polyester-based label

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